JP2012136405A - Laminate, multilayer glass, and method for producing laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate which is excellent in producibility, the transmission color tone of the laminate being an excellent gray color tone.SOLUTION: The laminate 1 includes, on its base material 2, a first transparent dielectric layer 31, a first infrared ray-reflecting layer 32, a first metal barrier layer 33, a second transparent dielectric layer 34, a second infrared ray-reflecting layer 35, a second metal barrier layer 36, and a third transparent dielectric layer 37, these layers being laminated in this order, and its transmission color tone is a gray color tone. The transparent dielectric layers 4 comprise a metal oxide whose main component is zinc oxide, and the metal barrier layers 6 comprise a metal whose main component is zinc. In addition, the metallic elements contained in the transparent dielectric layers 4 are the same as the metallic elements contained in the metal barrier layers 6, and the thickness of the first metal barrier layer 33 is larger than that of the second metal barrier layer 36.

Description

  The present invention relates to a laminate, a multilayer glass, and a method for producing a laminate, and more particularly to a laminate suitably used for a multilayer glass, a multilayer glass using the laminate, and a method for producing the laminate. .

  In recent years, the window glass of buildings such as buildings and houses, automobiles, trains, and other vehicles has been shielded from heat radiation from indoors to the outdoors during cold weather, or from outdoor to indoors when it is hot. For the purpose of improving indoor heat retention, improving cooling / heating efficiency, and saving energy, a glass laminate having a heat ray reflective film is being used. A glass laminate having such a heat ray reflective film has a low emissivity on the film surface and is called Low-E glass.

  For example, in a window glass used in a temperate area that does not require room heating as in a cold region, the flow of heat from the outside to the room is blocked and the heating of the room atmosphere by sunlight from the outside is suppressed. However, it is required to improve the cooling efficiency. Accordingly, two glass substrates are arranged so as to form a heat insulating air layer by sealing the peripheral edge, and a multilayer using a glass laminate having a heat ray reflective film on the heat insulating air layer side as the glass substrate on the outdoor side. Glass is becoming popular.

  As a heat ray reflective film, a transparent dielectric layer, an infrared reflective layer, and a transparent dielectric layer are sequentially laminated, and the transparent dielectric layer is mainly composed of zinc oxide, and the infrared reflective layer is mainly composed of silver ( For example, see Patent Document 1). In addition to such a three-layer type, a five-layer type in which a total of five layers of a transparent dielectric layer and an infrared reflective layer are laminated is also known (for example, see Patent Document 2).

  For such a glass laminate, the transmission color tone has a great influence on the appearance. Particularly for window glass for high-rise buildings, since the outer wall of a high-rise building generally has a gray color tone such as natural stone, the transmission color tone is required to be a gray color tone in relation to the surrounding color tone. Moreover, about a glass laminated body, it is calculated | required that it is a neutral color tone which does not become reddish etc. not only about a transmission color tone but a reflection color tone, for example, a reflection color tone when it sees from the outdoor. Furthermore, about the glass laminated body, from a viewpoint of improving productivity, it is calculated | required that there are few kinds and the number of layers of the structural layer which comprises a heat ray reflective film.

JP 2004-217432 A JP 7-165442 A

  The five-layered heat ray reflective film has a greater total thickness of the infrared reflective layer than the three-layered heat ray reflective film, and is excellent in heat shielding performance. In addition, when the transparent dielectric layer is mainly made of zinc oxide and the infrared reflecting layer is mainly made of silver, particularly when the metal barrier layer for suppressing the oxidation of the infrared reflecting layer is mainly made of zinc, good optical properties are obtained. In addition, the transparent dielectric layer and the metal barrier layer can be formed using the same metal target, resulting in excellent productivity.

  However, in the case where the transparent dielectric layer is mainly composed of zinc oxide, the infrared reflecting layer is mainly composed of silver, and the metal barrier layer is mainly composed of zinc, the transmission color tone is not necessarily grayish, particularly yellow and clear. It is not easy to make it gray. In particular, it is not easy to make the reflection color tone a neutral color tone while setting the transmission color tone to a gray color tone. By making the metal barrier layer from a metal material other than zinc, the transmission color tone can be a gray color tone and the reflection color tone can be a neutral color tone, but a target for forming the metal barrier layer separately. Is required, and the productivity tends to decrease.

  The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a laminate having a gray color tone that is excellent in productivity and has a good transmission color tone. It is also desirable to provide a laminate having a gray color tone with a good transmission color tone and a neutral color tone with a reflection color tone. Furthermore, this invention aims at providing the manufacturing method for manufacturing such a laminated body, and the multilayer glass which has such a laminated body.

  The first laminate of the present invention comprises a first transparent dielectric layer, a first infrared reflecting layer, a first metal barrier layer, a second transparent dielectric layer, and a second infrared reflecting on a transparent substrate. The layer, the second metal barrier layer, and the third transparent dielectric layer are laminated in this order, and the transmission color tone is a gray color tone.

  In the first laminate of the present invention, the transparent dielectric layer is composed of a layer mainly composed of zinc oxide, and the metal barrier layer is composed of a layer composed mainly of zinc, and is included in the transparent dielectric layer. The element other than oxygen and the element contained in the metal barrier layer are the same, and the thickness of the first metal barrier layer is larger than the thickness of the second metal barrier layer.

  The second laminate of the present invention comprises a first transparent dielectric layer, a first infrared reflection layer, a first metal barrier layer, a second transparent dielectric layer, and a second infrared reflection on a transparent substrate. The layer and the third transparent dielectric layer are laminated in this order, and the transmission color tone is a gray color tone.

  In the second laminate of the present invention, the transparent dielectric layer is composed of a layer mainly composed of zinc oxide, and the metal barrier layer is composed of a layer composed mainly of zinc, and is included in the transparent dielectric layer. The element other than oxygen and the element contained in the metal barrier layer are the same.

  In the method for producing a laminate of the present invention, a first transparent dielectric layer, a first infrared reflection layer, a first metal barrier layer, a second transparent dielectric layer, and a second infrared reflection are formed on a transparent substrate. The layer, the second metal barrier layer, and the third transparent dielectric layer are formed in this order to produce a laminate having a gray transmission color tone.

  The method for producing a laminate of the present invention uses the same metal target mainly composed of zinc for the formation of the transparent dielectric layer and the metal barrier layer, and the thickness of the first metal barrier layer before oxidation. The thickness of the second metal barrier layer is made thicker than that before oxidation.

  The multilayer glass of this invention has a transparent substrate and the laminated body arrange | positioned facing the said transparent substrate. The multilayer glass of the present invention is characterized in that the laminate is the laminate of the present invention described above.

  According to the laminate of the present invention, the transparent dielectric layer is mainly made of zinc oxide, the metal barrier layer is mainly made of zinc, and the elements other than oxygen contained in the transparent dielectric layer and the elements contained in the metal barrier layer Is substantially the same as that of the second metal barrier layer in the completed state after the formation of each layer, or by substantially increasing the thickness of the first metal barrier layer in the completed state after forming each layer. By providing only the first metal barrier layer without providing the second metal barrier layer, the transmission color tone can be changed to a gray color tone while being excellent in productivity.

  Further, according to the method for manufacturing a laminate of the present invention, the same metal target mainly composed of zinc is used for forming the transparent dielectric layer and the metal barrier layer, and the thickness of the first metal barrier layer before oxidation is determined. By making the thickness thicker than the thickness of the second metal barrier layer before oxidation, it is possible to efficiently manufacture a laminate having a transmission color tone of gray.

  Furthermore, according to the multilayer glass of the present invention, by using the laminate of the present invention, the transmission color tone can be changed to a gray color tone while being excellent in productivity.

The typical sectional view showing an example of the 1st layered product of the present invention. The typical sectional view showing an example of the 2nd layered product of the present invention. The typical sectional view showing an example of the multilayer glass of the present invention. The figure which shows distribution of the transmission color tone of each laminated body in an Example. The figure which shows distribution of the reflective color tone by the side of the transparent base | substrate of each laminated body in an Example.

  Hereinafter, embodiments of the laminate of the present invention will be described.

  FIG. 1 is a schematic cross-sectional view showing an example of the first laminated body. The first laminate 1 has a heat ray reflective film 3 on a transparent substrate 2. The heat ray reflective film 3 includes, in order from the transparent substrate 2 side, a first transparent dielectric layer 31, a first infrared reflective layer 32, a first metal barrier layer 33, a second transparent dielectric layer 34, and a second transparent dielectric layer 34. The infrared reflection layer 35, the second metal barrier layer 36, and the third transparent dielectric layer 37 are laminated. In the following description, the transparent dielectric layers are collectively referred to as a transparent dielectric layer 4, the infrared reflection layers are collectively referred to as an infrared reflection layer 5, and the metal barrier layers are collectively referred to as a metal barrier layer 6. To do.

  In the first laminate 1, the transparent dielectric layer 4 is composed of a layer containing zinc oxide as a main component, the metal barrier layer 6 is composed of a layer containing zinc as a main component, and other than oxygen contained in the transparent dielectric layer 4. And the element contained in the metal barrier layer 6 are the same, and the thickness of the first metal barrier layer 33 is greater than the thickness of the second metal barrier layer 36. In addition, the thickness in this invention means geometric thickness.

  According to such a laminate 1, the transparent dielectric layer 4 and the metal barrier layer 6 can be formed by sputtering using the same metal target, reducing the types of targets necessary for sputtering, and improving productivity. It can be made excellent. Further, by setting the thickness of the first metal barrier layer 33 to be larger than the thickness of the second metal barrier layer 36, the transmission color tone is changed to a gray tone, particularly a clear gray tone without yellowness. Can do.

  The gray tone means that the chromaticity in the chromaticity coordinates defined in JIS Z8701 is in the range of x = 0.300 to 0.315 and y = 0.324 to 0.333. To do. Such a range of chromaticity is adopted because it appears to be a clear gray tone without yellowishness in many ordinary people.

  FIG. 2 is a schematic cross-sectional view showing an example of the second laminate 1. As shown in FIG. 2, the second metal barrier layer 36 is not necessarily formed. That is, the heat ray reflective film 3 includes, in order from the transparent substrate 2 side, the first transparent dielectric layer 31, the first infrared reflective layer 32, the first metal barrier layer 33, the second transparent dielectric layer 34, the first Two infrared reflective layers 35 and a third transparent dielectric layer 37 may be laminated.

  In the second laminate 1 as well, the transparent dielectric layer 4 is composed of a layer mainly composed of zinc oxide, and the metal barrier layer 6 is composed of a layer composed mainly of zinc, and is included in the transparent dielectric layer 4. The element other than oxygen and the element contained in the metal barrier layer 6 are the same.

  For the second laminate 1 as well, the transparent dielectric layer 4 and the metal barrier layer 6 can be formed by sputtering using the same metal target, reducing the types of targets necessary for sputtering, and improving productivity. It can be excellent. Further, by providing only the first metal barrier layer 33 without providing the second metal barrier layer 36, the transmission color tone can be a gray tone, particularly a clear gray tone without yellowness. .

  The transparent substrate 2 in the laminate 1 can be a glass substrate such as soda lime glass or non-alkali glass. Although the thickness of the transparent base | substrate 2 is not specifically limited, Usually, 1-10 mm is preferable.

  The transparent dielectric layer 4 is composed of a layer mainly composed of zinc oxide. The layer mainly composed of zinc oxide is a layer composed solely of zinc oxide, or contains zinc oxide as a main component, and is selected from tin, aluminum, chromium, titanium, silicon, boron, magnesium, and gallium as an additive element. Examples include a layer containing at least one kind.

  The inclusion of the additive element is preferable because internal stress can be reduced and adhesion with the transparent substrate 2 and the like can be improved. As the additive element, aluminum and tin are particularly preferable. A material containing either aluminum or tin is preferable because the compatibility with the infrared reflective layer 5 can be improved. Aluminum is an inexpensive material and is preferable because the film formation rate is high. Tin is also preferable because it is a relatively inexpensive material.

  In the case where the additive element is included, if the content is too large, the stability of the infrared reflective layer 5 formed on the transparent dielectric layer 4 may be lowered. For this reason, 1-10 mass% is preferable with respect to the total amount of the zinc in the transparent dielectric layer 4, and an additional element, and, as for content of the said additional element, 2-6 mass% is more preferable.

  Each transparent dielectric layer 4 contains the same element. Here, the phrase “containing the same element” means that the types of elements to be contained, that is, combinations are the same. Therefore, when the additive element is contained, each transparent dielectric layer 4 contains the same additive element. Each transparent dielectric layer 4 preferably further has the same content of each constituent element from the viewpoint of productivity.

  The transparent dielectric layer 4 contains the same elements as the elements contained in the metal barrier layer 6 except for oxygen. According to such a thing, the transparent dielectric material layer 4 and the metal barrier layer 6 can be formed by sputtering using the same metal target, and the type of target required for sputtering is reduced as a whole, and productivity is reduced. It can be made excellent. In the transparent dielectric layer 4, it is preferable that the content ratio of the constituent elements excluding oxygen is the same as the content ratio of the constituent elements in the metal barrier layer 6 from the viewpoint of productivity.

  The transparent dielectric layer 4 preferably has the largest thickness of the second transparent dielectric layer 34, and the difference between the thickness of the first transparent dielectric layer 12 and the thickness of the third transparent dielectric layer 18. Is preferably 100 mm or less. In addition, the thickness in description of the laminated body 1 (except description of the manufacturing method mentioned later) means the substantial thickness in the completion state after each layer formation. For example, the thickness of the transparent dielectric layer 4 in the laminate 1 is such that the portion formed as the transparent dielectric layer 4 and the metal barrier layer 6 formed before it are oxidized to form the transparent dielectric layer 4 and Both parts are included.

  The thickness of the first transparent dielectric layer 31 is preferably 290 to 470 mm, and more preferably 295 to 465 mm. The thickness of the second transparent dielectric layer 34 is preferably 660 to 1035 mm, more preferably 665 to 1035 mm, particularly preferably 800 to 1035 mm, and more preferably 805 to 1030 mm. The thickness of the third transparent dielectric layer 37 is preferably 300 to 465 mm, and more preferably 305 to 465 mm.

  By setting the thickness of each transparent dielectric layer 4 within the above range, the transmission color tone can be a gray tone, particularly a clear gray tone without yellowness. In particular, by setting the thickness of the second transparent dielectric layer 34 to 660 mm or more, it is easy to make the transmission color tone gray, and by setting the thickness of the second transparent dielectric layer 34 to 800 mm or more, The transmission color tone is changed to a gray color tone, and the reflection color tone on the transparent substrate 2 side is easily set to a neutral color tone.

  Conventionally, in the heat ray reflective film, since the neutral color or blue color is relatively preferred, it has been performed to adjust the color tone to these ranges, but with the above-described film configuration with excellent productivity, In order to achieve a clear gray color, it is necessary to cut a light yellow or green wavelength which is the original transmission color tone of the material, and the reflection color tone must be light yellow or green. On the other hand, when the glass is viewed from the outdoor side, when the reflection color is neutral or blue, it is combined with high merchantability, and while maintaining the glass surface reflection color neutral, the film surface reflection color Needs to be pale yellow or green, and by satisfying this unbalanced characteristic, it becomes possible to achieve a clear gray color for the first time. The inventor of the present invention has found the above-mentioned film thickness range as a result of intensive studies in order to realize that one transparent laminate exhibits different types of reflection colors depending on the front and back sides.

  The neutral color tone means that the chromaticity in the chromaticity coordinates defined in JIS Z8701 is in the range of x = 0.280 to 0.340 and y = 0.290 to 0.385. To do. Such a range of chromaticity is adopted because many ordinary people have no reddish color and seem to have a clear neutral tone.

  The infrared reflecting layer 5 is preferably made of a layer containing silver as a main component. As a layer which has silver as a main component, the layer which consists only of silver, or the layer which has silver as a main component and contains at least 1 sort (s) chosen from palladium, gold | metal | money, and platinum as an additional element is mentioned. According to what contains the said additive element, while improving infrared reflective performance, absorption of visible light can be suppressed and stability of silver can also be improved.

  In the case where the additive element is contained, if the content ratio is too large, the film formation rate and the visible light transmittance may be decreased, and the emissivity may be increased. For this reason, the content of the additive element is preferably 0.1 to 10% by mass, more preferably 0.1 to 5.0% by mass, based on the total amount of silver and additive elements in the infrared reflective layer 5. More preferably, it is 3 to 2.0% by mass.

  In addition, it is preferable that the elements contained in each infrared reflective layer 5 are substantially the same. According to such a thing, each infrared reflective layer 5 can be formed by sputtering using the same metal target, and as a whole, the types of targets necessary for sputtering are reduced and the productivity is excellent. be able to.

  The thickness of the first infrared reflective layer 32 is preferably 80 to 130 mm, and more preferably 80 to 125 mm. The thickness of the second infrared reflective layer 35 is preferably 95 to 160 mm, and more preferably 95 to 155 mm. In particular, the thickness of the first infrared reflection layer 32 is the same as the thickness of the second infrared reflection layer 35 or the thickness of the second infrared reflection layer 35 is larger than the thickness of the first infrared reflection layer 32. The thickness difference between the first infrared reflection layer 32 and the second infrared reflection layer 35 is preferably 0 to 55 mm, and more preferably 0 to 50 mm. By setting it to such a thickness, the transmission color tone can be easily set to a gray color tone, and the reflection color tone on the transparent substrate 2 side can be easily set to a neutral color tone.

  The metal barrier layer 6 is composed of a layer mainly composed of zinc. The layer containing zinc as a main component includes at least one layer selected from tin, aluminum, chromium, titanium, silicon, boron, magnesium, and gallium as an additive element. The layer containing is mentioned. According to such a metal barrier layer 6, it can be formed by sputtering using the same metal target as the transparent dielectric layer 4, reduces the types of targets required for sputtering, and has excellent productivity. can do.

  When the additive element is included, if the content is too high, the stability of the infrared reflective layer 5 formed on the transparent dielectric layer 4 may be reduced when the transparent dielectric layer 4 is formed using the same metal target. There is. For this reason, 1-10 mass% is preferable with respect to the total amount of zinc and an additional element in the metal barrier layer 6, and, as for content of the said additional element, 2-6 mass% is more preferable.

  Each metal barrier layer 6 contains the same element. Each metal barrier layer 6 preferably further has the same content of each constituent element from the viewpoint of productivity. The metal barrier layer 6 contains the same element as the element other than oxygen contained in the transparent dielectric layer 4. From the viewpoint of productivity, the metal barrier layer 6 preferably further has the same constituent element content ratio as the constituent element content ratio of the transparent dielectric layer 4 excluding oxygen.

  The thickness of the first metal barrier layer 33 is preferably 10 to 80 mm, and more preferably 15 to 75 mm. Further, the thickness of the second metal barrier layer 36 is preferably 2.0 mm or less, and more preferably 1.0 mm or less. The thickness of the second metal barrier layer 36 is 0 mm, that is, the second metal barrier layer 36 may not be formed. By setting it to such a thickness, the transmission color tone can be made a gray tone, particularly a clear gray tone without yellowishness.

  The laminated body 1 can have a protective layer (not shown) in order to improve the durability of the heat ray reflective film 3 formed on the transparent substrate 2. An example of the protective layer is a tin oxide layer containing silicon. A tin oxide layer containing silicon is preferable because it has good compatibility with a layer containing zinc oxide as a main component, and strong adhesion can be obtained at the interface. The content ratio of silicon to the total amount of tin and silicon in the tin oxide layer containing silicon is preferably 5 to 95% by mass, more preferably 30 to 90% by mass, and still more preferably 40 to 90% by mass.

  In the laminated body 1, the above-described heat ray reflective film 3, that is, the first transparent dielectric is formed on the transparent substrate 2 from the viewpoint of reducing the types of targets necessary for sputtering and improving productivity. Body layer 31, first infrared reflective layer 32, first metal barrier layer 33, second transparent dielectric layer 34, second infrared reflective layer 35, second metal barrier layer 36, and third transparent dielectric It is preferable to have only the body layer 37 and no other layers.

  The visible light transmittance Tv in such a laminate 1 is preferably 50 to 70%, more preferably 52 to 68%, and still more preferably 53 to 67%. Further, the solar transmittance Te is preferably 25 to 35%, and more preferably 26 to 34%. The visible light transmittance Tv and the solar radiation transmittance Te are obtained in accordance with the provisions of JIS R3106 by measuring the transmittance and reflectance in the wavelength range of 300 to 2500 nm with a spectrophotometer.

The laminate 1 of the present invention can be suitably used as a multi-layer glass.
FIG. 3 shows an example of the multilayer glass 10. The multilayer glass 10 has a transparent substrate 11 made of a glass substrate or the like facing the laminated body 1, and an intermediate air layer 12 is formed between the laminated body 1 and the transparent substrate 11. A spacer 13 is disposed on the surface. The laminated body 1 is disposed on the outdoor side with respect to the transparent substrate 11, and the heat ray reflective film 3 is disposed so as to face the transparent substrate 11.

  For example, argon gas is sealed in the intermediate air layer 12. A primary sealing material 14 seals between the laminate 1 and the spacer 13 and between the transparent substrate 11 and the spacer 13. Further, the peripheral edge between the laminate 1 and the transparent substrate 11 is sealed with a secondary sealing material 15. A space 131 is provided inside the spacer 13, and a hole 132 that connects the space 131 and the intermediate air layer 12 is provided. In the space 131, in order to suppress condensation in the intermediate air layer 12. The desiccant 16 is filled.

  The visible light transmittance Tv of the multilayer glass 10 is preferably 45 to 55%, and more preferably 47 to 53%. Moreover, 10-20% is preferable and, as for visible light reflectance Rv by the side of the laminated body 1, 12-16% is more preferable. Furthermore, the solar radiation acquisition rate is preferably 0.25 to 0.35, and more preferably 0.27 to 0.34.

Next, the manufacturing method of the laminated body 1 of this invention is demonstrated.
In the method for manufacturing the laminate 1 of the present invention, the first transparent dielectric layer 31, the first infrared reflection layer 32, the first metal barrier layer 33, and the second as the heat ray reflective film 3 on the transparent substrate 2. The transparent dielectric layer 34, the second infrared reflection layer 35, the second metal barrier layer 36, and the third transparent dielectric layer 37 are formed in this order.

  In the manufacturing method of the laminate 1 of the present invention, in particular, the same metal target mainly composed of zinc is used for forming the transparent dielectric layer 4 and the metal barrier layer 6, and before the first metal barrier layer 33 is oxidized. Is made thicker than the thickness of the second metal barrier layer 36 before oxidation. The thickness before oxidation of the metal barrier layer 6 means the thickness in an unoxidized state before the transparent dielectric layer 4 is formed, that is, the thickness immediately after the metal barrier layer 6 is formed. .

  According to the method for manufacturing the laminate 1 of the present invention, the same metal target mainly composed of zinc is used for film formation of the transparent dielectric layer 4 and the metal barrier layer 6, so that the type of target necessary for sputtering can be changed. Can be reduced and productivity can be improved. In addition, by setting the thickness of the first metal barrier layer 33 before oxidation to be greater than the thickness of the second metal barrier layer 36 before oxidation, the transmission color tone can be a gray color tone.

  The laminated body 1 is manufactured, for example, by sputtering such as DC sputtering or AC sputtering using an in-line type sputtering apparatus on the transparent substrate 2 made of a glass substrate or the like, the transparent dielectric layer 4, the infrared reflecting layer 5, the metal barrier. This can be done by forming the layer 6.

  At this time, the transparent dielectric layer 4 is sputtered in an atmosphere containing, for example, argon and oxygen, and the metal barrier layer 6 is sputtered in an atmosphere consisting of, for example, only argon that does not contain oxygen. The layers can be formed using the same metal target. Further, the thickness of the metal barrier layer 6 before oxidation can be performed by adjusting a substantial film formation time.

  As a metal target used for forming the transparent dielectric layer 4 and the metal barrier layer 6, one having zinc as a main component is used. The metal target mainly composed of zinc includes at least zinc, or contains zinc as a main component, and the additive element is at least selected from tin, aluminum, chromium, titanium, silicon, boron, magnesium, gallium, and the like The thing containing 1 type of elements is mentioned. As the additive element, aluminum and tin are particularly preferable. A material containing either aluminum or tin is preferable because the transparent dielectric layer 4 having excellent compatibility with the infrared reflective layer 5 can be obtained.

  In the case where the additive element is included, if the content is too large, the stability of the infrared reflective layer 5 formed on the transparent dielectric layer 4 may be lowered. For this reason, 1-10 mass% is preferable with respect to the total amount of zinc and an additional element in a metal target, and, as for content of the said additional element, 2-6 mass% is more preferable.

  The thickness of the first transparent dielectric layer 31 is preferably 290 to 470 mm, and more preferably 295 to 465 mm. The thickness of the second transparent dielectric layer 34 is preferably 650 to 1020 mm, more preferably 655 to 1020 mm, particularly preferably 790 to 1020 mm, and more preferably 795 to 1015 mm. The thickness of the third transparent dielectric layer 37 is preferably 290 to 450 mm, and more preferably 295 to 450 mm.

  Note that the thickness of the transparent dielectric layer 4 in the description of the manufacturing method does not include an increase due to oxidation of the metal barrier layer 6, in other words, the thickness of the transparent dielectric layer 4 to be formed by film formation itself. Is the thickness. Therefore, the preferable thickness of the transparent dielectric layer 4 in the description of the manufacturing method, particularly the preferable thicknesses of the second transparent dielectric layer 34 and the third transparent dielectric layer 37 are the thicknesses in the laminated body 1 already described. Unlike Sato, it is slightly thinner. On the other hand, the preferable thicknesses of the following first metal barrier layer 33 and second metal barrier layer 36 (both before oxidation) are slightly thicker than the thicknesses of the laminated body 1 already described. .

  Ratio of thickness before oxidation of first metal barrier layer 33 to thickness before oxidation of second metal barrier layer 36 (thickness before oxidation of first metal barrier layer 33 / second metal barrier layer) The thickness of 36 before oxidation) is preferably 2.0 to 7.0, and more preferably 2.3 to 6.0. By setting such a thickness ratio, it is possible to make the transmission color tone particularly a gray color tone, particularly a clear gray color tone without yellowness.

  The thickness of the first metal barrier layer 33 before oxidation is preferably 20 to 95 mm, particularly preferably 25 to 95 mm, and more preferably 30 to 90 mm. Further, the thickness of the second metal barrier layer 36 before oxidation is preferably 5 to 20 mm, and more preferably 7 to 18 mm. By setting it to such a thickness, oxidation of each infrared reflective layer 5 can be effectively suppressed, and in addition to the thickness ratio described above, the transmission color tone is particularly clear with no gray tone, particularly yellowishness. Can be a gray tone.

  As a metal target used for film formation of the infrared reflective layer 5, a metal target containing silver as a main component is preferable. As what has silver as a main component, what consists only of silver, or the thing which has at least 1 sort (s) chosen from palladium, gold | metal | money, and platinum as an additive element which has silver as a main component is mentioned. A material containing the additive element is preferable because it has high infrared reflection performance, little visible light absorption, and high silver stability.

  In the case where the additive element is contained, if the content ratio is too large, the film formation rate and the visible light transmittance may be decreased, and the emissivity may be increased. For this reason, the content of the additive element is preferably 0.1 to 10% by mass, more preferably 0.1 to 5.0% by mass, based on the total amount of silver and additive elements in the infrared reflective layer 5. More preferably, it is 3 to 2.0% by mass.

  The thickness of the first infrared reflective layer 32 is preferably 80 to 130 mm, and more preferably 80 to 125 mm. The thickness of the second infrared reflective layer 35 is preferably 95 to 160 mm, and more preferably 95 to 155 mm. In particular, the thickness of the first infrared reflection layer 32 is the same as the thickness of the second infrared reflection layer 35 or the thickness of the second infrared reflection layer 35 is larger than the thickness of the first infrared reflection layer 32. The thickness difference between the first infrared reflection layer 32 and the second infrared reflection layer 35 is preferably 0 to 55 mm, and more preferably 0 to 50 mm.

  Hereinafter, the present invention will be specifically described with reference to examples.

(Sample Nos. 1-1 to 1-9, 2)
A laminate having the structure shown in Table 1 was manufactured. That is, a glass substrate (FL3, 100 mm × 100 mm × 3 mmt) was used as the transparent substrate, and an infrared reflective film was formed by DC sputtering. Sample No. Each of the metal barrier layers 1-1 to 1-9 (Al: Zn) is actually oxidized to a thickness of 9 mm when the transparent oxide layer (transparent dielectric layer) is formed, and the thickness is increased accordingly. Decrease. On the other hand, the thickness of the adjacent transparent oxide layer (Al: ZnO) increases by this amount. Table 2 shows the thicknesses of the first and second metal barrier layers (Al: Zn (1), Al: Zn (2)) before and after oxidation, the thickness ratio before oxidation, and before (after) oxidation. The difference in thickness is shown together.

In an in-line type sputtering apparatus used for sputtering, each sputtering target composed of an AlZn alloy containing 2% by mass of Al, a PdAg alloy containing 1% by mass of Pd, and a NiCr alloy is formed on a cathode in a film forming chamber. installed. In addition, each layer of the infrared reflective film was formed by introducing the cleaned glass substrate into the load lock chamber, evacuating the entire vacuum chamber to 2.0 × 10 ⁻⁴ Pa, and performing the following steps.

<Transparent oxide layer (Al: ZnO)>
Argon and oxygen were introduced into the vacuum chamber at 30:70 sccm as discharge gases, and formed by reactive DC magnetron sputtering of a sputtering target made of an AlZn alloy containing 2% by mass of Al. The sputtering target was 70 × 200 mm ² and 500 W was applied as the sputtering power. At this time, the pressure in the vacuum chamber was 0.4 Pa.

<Infrared reflective layer (PdAg)>
Argon was introduced at 100 sccm as a discharge gas into the vacuum chamber, and the sputtering target was formed by DC magnetron sputtering made of a PdAg alloy containing 1% by mass of Pd. The sputtering target was 70 × 200 mm ² and 100 W was applied as the sputtering power. At this time, the pressure in the vacuum chamber was 0.4 Pa.

<Metal barrier layer (Al: Zn)>
Argon was introduced as a discharge gas at 100 sccm in a vacuum chamber, and a target composed of an AlZn alloy containing 2 mass% Al or a target composed of NiCr was formed by DC magnetron sputtering. The sputtering target was 70 × 200 mm ² and 15 W was applied as the sputtering power. At this time, the pressure in the vacuum chamber was 0.4 Pa.

(Sample Nos. 3-1 to 3-6)
A laminate having the structure shown in Table 1 was manufactured. That is, a glass substrate (FL6, 100 mm × 100 mm × 6 mmt) was used as a transparent substrate, and an infrared reflective film was formed by DC sputtering or AC sputtering. Sample No. Each of the metal barrier layers 3-1 to 3-6 (Al: Zn) is actually oxidized with a thickness of 14.5 mm when the transparent oxide layer is formed, and the thickness is reduced accordingly. On the other hand, the thickness of the adjacent transparent oxide layer (Al: ZnO) increases by this amount. Table 2 shows the thicknesses of the first and second metal barrier layers (Al: Zn (1), Al: Zn (2)) before and after oxidation, the thickness ratio before oxidation, and before (after) oxidation. The difference in thickness is shown together.

In the in-line type sputtering apparatus used for sputtering, each sputtering target made of an AlZn alloy containing 2% by mass of Al and a PdAg alloy containing 1% by mass of Pd was placed on the cathode in the film forming chamber. In addition, each layer of the infrared reflective film was formed by introducing the cleaned glass substrate into the load lock chamber, evacuating the entire vacuum chamber to 6.0 × 10 ⁻⁴ Pa, and performing the following steps.

<Transparent oxide layer (Al: ZnO)>
Argon and oxygen were introduced into the vacuum chamber at 1000: 900 sccm as discharge gases, and formed by reactive AC magnetron sputtering of a sputtering target made of an AlZn alloy containing 2% by mass of Al. The sputter target was a 1778 mm long tube type, and 30 kW was applied as the sputtering power. At this time, the pressure in the vacuum chamber was 0.7 Pa.

<Infrared reflective layer (PdAg)>
Argon was introduced into the vacuum chamber at 1000 sccm as a discharge gas, and formed by DC magnetron sputtering of a sputtering target made of a PdAg alloy containing 1% by mass of Pd. The sputtering target was 100 × 1700 mm ² and 3 kW was applied as the sputtering power. At this time, the pressure in the vacuum chamber was 0.5 Pa.

<Metal barrier layer (Al: Zn)>
Argon was introduced into the vacuum chamber as a discharge gas at 1000 sccm, and the target was formed by DC magnetron sputtering of a target made of an AlZn alloy containing 2% by mass of Al. The sputter target was a 1778 long tube type, and 1 kW was applied as the sputtering power. At this time, the pressure in the vacuum chamber was 0.45 Pa.

  About these laminated bodies, the transmittance | permeability and reflectance between wavelengths 300-2500nm were measured with the spectrophotometer (made by Shimadzu Corporation, UV3100), and visible light transmittance | permeability Tv (%) and solar radiation transmission according to prescription | regulation of JISR3106. The rate Te (%) and the visible light reflectance Rv (%) on the glass substrate side and the infrared reflection film side were determined. Further, according to JIS Z8701, the transmission color tone (x, y) and the reflection color tone (x, y) on the glass substrate side and the infrared reflection film side were determined. The light source was a D65 light source and a 10 degree viewing angle. Table 3 shows the performance of each laminate. In addition, among the results in Table 3, the results of the transmission color tone (x, y) and the reflection color tone (x, y) on the glass substrate side are collectively shown in FIGS.

  Among these laminates, samples having a transmission color tone of gray are shown in Sample No. It is a laminate of 1-1, 1-2, 1-5, 1-9, 3-1 to 3-6. Of these, samples with a reflective color tone on the glass substrate side having a neutral color tone are sample Nos. It is a laminated body of 1-2, 1-5, 1-9, 3-1 to 3-6. Sample No. In No. 2, the transmission color tone is a gray color tone and the reflection color tone on the glass substrate side is a neutral color tone, but the metal barrier layer is made of a NiCr alloy and is not necessarily excellent in productivity.

  From these results, it is necessary to make at least the thickness before oxidation of the first metal barrier layer larger than the thickness before oxidation of the second metal barrier layer in order to make the transmission color tone gray. I understand. In addition, it can be seen that the thickness of the second transparent dielectric layer 34 is preferably 650 mm or more in order to make the transmission color tone a gray color tone. Here, the thickness of the second transparent dielectric layer 34 does not include an increase due to oxidation of the metal barrier layer.

  In order to make the reflection color tone on the glass substrate side a neutral color tone while setting the transmission color tone to a gray color tone, it is effective to set the thickness of the second transparent dielectric layer 34 to 790 mm or more. Recognize.

(Multilayer glass)
Sample No. A laminated glass of 3-3 to 3-6 was used, and a glass substrate having a thickness of 6 mm was used as an opposing transparent substrate, and a multilayer glass having an intermediate air layer of 12 mm was produced. About this multilayer glass, the transmittance | permeability and reflectance between wavelengths 300-2500nm are measured with a spectrophotometer (made by Shimadzu Corporation, UV3100), and the visible light transmittance Tv and the visible light on the laminated body side are defined according to JIS R3106. The reflectance Rv and the solar heat acquisition rate were determined. The results are shown in Table 4.

  DESCRIPTION OF SYMBOLS 1 ... Laminated body, 2 ... Transparent base material, 3 ... Heat ray reflective film, 4 ... Transparent dielectric layer, 5 ... Infrared reflective layer, 6 ... Metal barrier layer, 10 ... Multi-layer glass, 11 ... Transparent substrate, 31st DESCRIPTION OF SYMBOLS 1 transparent dielectric layer, 32 ... 1st infrared reflective layer, 33 ... 1st metal barrier layer, 34 ... 2nd transparent dielectric layer, 35 ... 2nd infrared reflective layer, 36 ... 2nd metal Barrier layer, 37 ... third transparent dielectric layer

Claims (9)

On the transparent substrate, a first transparent dielectric layer, a first infrared reflecting layer, a first metal barrier layer, a second transparent dielectric layer, a second infrared reflecting layer, a second metal barrier layer, and The third transparent dielectric layer is laminated in this order, and the laminated body has a transmission color tone of gray,
The transparent dielectric layer is a layer containing zinc oxide as a main component, the metal barrier layer is a layer containing zinc as a main component, and an element other than oxygen contained in the transparent dielectric layer and the metal barrier layer The laminated body, wherein the elements included are the same, and the thickness of the first metal barrier layer is thicker than the thickness of the second metal barrier layer.   The laminate according to claim 1, wherein the thickness of the first metal barrier layer is 10 to 80 mm, and the thickness of the second metal barrier layer is 2.0 mm or less. On the transparent substrate, a first transparent dielectric layer, a first infrared reflective layer, a first metal barrier layer, a second transparent dielectric layer, a second infrared reflective layer, and a third transparent dielectric layer Are laminated in this order, and the transparent color tone is a gray color tone,
The transparent dielectric layer is a layer containing zinc oxide as a main component, the metal barrier layer is a layer containing zinc as a main component, and an element other than oxygen contained in the transparent dielectric layer and the metal barrier layer A laminate comprising the same elements.   The laminate according to claim 3, wherein the thickness of the first metal barrier layer is 10 to 80 mm.   The laminated body according to any one of claims 1 to 4, wherein a reflection color tone of the transparent substrate side surface is a neutral color tone. On the transparent substrate, a first transparent dielectric layer, a first infrared reflecting layer, a first metal barrier layer, a second transparent dielectric layer, a second infrared reflecting layer, a second metal barrier layer, and A method for producing a laminate in which a third transparent dielectric layer is formed in this order, and a laminate having a gray transmission color tone is produced,
The same metal target mainly composed of zinc is used for forming the transparent dielectric layer and the metal barrier layer, and the thickness of the first metal barrier layer is set to the thickness of the second metal barrier layer. A method for producing a laminate, wherein the thickness is greater than the thickness before oxidation.   The lamination according to claim 6, wherein a ratio of a thickness of the first metal barrier layer before oxidation to a thickness of the second metal barrier layer before oxidation is set to 2.0 to 7.0. Body manufacturing method.   8. The laminate according to claim 6, wherein the thickness of the first metal barrier layer before oxidation is 20 to 95 mm, and the thickness of the second metal barrier layer before oxidation is 5 to 20 mm. Body manufacturing method. A multi-layer glass having a transparent substrate and a laminate disposed to face the transparent substrate,
A multilayer glass, wherein the laminate is a laminate according to any one of claims 1 to 5.

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