JPH03275533A - Heat ray shielding glass - Google Patents
Heat ray shielding glassInfo
- Publication number
- JPH03275533A JPH03275533A JP7419090A JP7419090A JPH03275533A JP H03275533 A JPH03275533 A JP H03275533A JP 7419090 A JP7419090 A JP 7419090A JP 7419090 A JP7419090 A JP 7419090A JP H03275533 A JPH03275533 A JP H03275533A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- glass
- refractive index
- heat ray
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011521 glass Substances 0.000 title claims abstract description 48
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 150000004767 nitrides Chemical class 0.000 claims abstract description 26
- 229910052726 zirconium Inorganic materials 0.000 claims abstract 3
- 239000004408 titanium dioxide Substances 0.000 claims description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- 239000001301 oxygen Substances 0.000 claims description 18
- 238000002834 transmittance Methods 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 239000010955 niobium Substances 0.000 claims description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 8
- 239000011248 coating agent Substances 0.000 abstract description 7
- 230000007935 neutral effect Effects 0.000 abstract description 7
- 230000003287 optical effect Effects 0.000 abstract description 5
- 229910052719 titanium Inorganic materials 0.000 abstract description 5
- 239000006121 base glass Substances 0.000 abstract 2
- 229910052804 chromium Inorganic materials 0.000 abstract 1
- 229910052735 hafnium Inorganic materials 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 17
- 239000002184 metal Substances 0.000 description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 238000004544 sputter deposition Methods 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000005357 flat glass Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 5
- 239000005329 float glass Substances 0.000 description 4
- 238000005546 reactive sputtering Methods 0.000 description 4
- 229910000906 Bronze Inorganic materials 0.000 description 3
- 229910000676 Si alloy Inorganic materials 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 239000010974 bronze Substances 0.000 description 3
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 235000006679 Mentha X verticillata Nutrition 0.000 description 2
- 235000002899 Mentha suaveolens Nutrition 0.000 description 2
- 235000001636 Mentha x rotundifolia Nutrition 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910001257 Nb alloy Inorganic materials 0.000 description 1
- 229910001362 Ta alloys Inorganic materials 0.000 description 1
- 229910007948 ZrB2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- LKTZODAHLMBGLG-UHFFFAOYSA-N alumanylidynesilicon;$l^{2}-alumanylidenesilylidenealuminum Chemical compound [Si]#[Al].[Si]#[Al].[Al]=[Si]=[Al] LKTZODAHLMBGLG-UHFFFAOYSA-N 0.000 description 1
- VWZIXVXBCBBRGP-UHFFFAOYSA-N boron;zirconium Chemical compound B#[Zr]#B VWZIXVXBCBBRGP-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000004313 glare Effects 0.000 description 1
- 239000005340 laminated glass Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Landscapes
- Surface Treatment Of Glass (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は可視光線透過率が高（、日射透過率が低い熱線
造幣ガラスに関し、とりわけ自動車の窓ガラス１こ適し
た単板ガラスとして使用しうる熱線造幣ガラスに関する
。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a hot-ray minted glass having a high visible light transmittance (and a low solar transmittance), which can be used as a single glass particularly suitable for automobile window glass. Regarding hot wire minted glass.
［従来の技術］
自動車の窓ガラスを通して車内に流入する太陽光のエネ
ルギーを造幣し、車内の温度上昇を防止して、冷房負荷
を低減させる目的で、熱線造幣ガラスを窓ガラスに採用
することが増えてきている。[Conventional technology] Heat-ray minted glass can be used in window glass for the purpose of converting the energy of sunlight that flows into the interior of a car through the window glass, preventing a rise in temperature inside the car, and reducing the cooling load. It is increasing.
しかしながら自動車の窓ガラスとしては、安全性の確保
から高い視認性を確保するために可視光線透過率は７０
％以上であることが要求されている。However, in order to ensure safety and high visibility, the visible light transmittance of automobile window glass is 70.
% or more.
このような要求を満足する熱線造幣ガラスとしては、米
国特許第４３３７９９０号で開示されているようなＡｇ
膜を透明な酸化物の膜でサントイ・ノチした構造の膜を
被覆したガラスがある。さらに、ＴＩＮのごとき金属窒
化物の膜を、二酸化チタンなどの高屈折率の透明酸化物
の膜ではさんだ熱線造幣膜が、 ５ＰＩＥ Ｖｏｌ
、３２４．ｐ５２〜５／７ 、１９８２ （Ｏｐｔｉｃ
ａｌ Ｃｏａｔｉｎｇｓ ｆｏｒ Ｅｎｅｒｇｙ Ｅｒ
ｒｉｃｉｅｎｃｙ ａｎｄ ５ｏｌａｒ Ａｐｐｌｉｃ
ａｔｉｏｎｓ）に開示されている。As a hot-wire minted glass that satisfies such requirements, Ag as disclosed in U.S. Pat. No. 4,337,990 is available.
There is glass that is coated with a transparent oxide film with a thin structure. Furthermore, a hot ray mint film in which a metal nitride film such as TIN is sandwiched between a film of a transparent oxide with a high refractive index such as titanium dioxide, is 5PIE Vol.
, 324. p52~5/7, 1982 (Optic
al Coatings for Energy
riciency and 5olar Applic
ations).
［発明が解決しようとする課題］
しかし前記したＡｇ膜を用いる熱線造幣ガラス〆は、化
学的耐久性や耐摩耗性に劣っているので、合わせガラス
などのように膜を外部に触れない状態で用いなければな
らない。しかしながら自動車のリアガラスやサイドガラ
スは単板ガラスで使用されるので、前記したＡｇ膜を用
いた熱線造幣ガラスは使用できないという問題があった
。[Problems to be Solved by the Invention] However, the heat-wire minted glass using the above-mentioned Ag film has poor chemical durability and abrasion resistance, so unlike laminated glass, the film cannot be exposed to the outside. must be used. However, since the rear glass and side glass of automobiles are used as single glass, there is a problem in that the above-mentioned hot wire minted glass using an Ag film cannot be used.
また、前記した金属の窒化物の膜を用いた熱線造幣ガラ
スでは、良好な熱線造幣性能がえられる膜の厚みの組合
せでは、反射色調が赤色ないしは紫色になってしまうと
いう問題があった。Further, in the hot wire minting glass using the metal nitride film described above, there is a problem in that the reflected color tone becomes red or purple when the combination of film thicknesses provides good hot wire minting performance.
本発明は良好な熱線造幣性能と高い可視光線透過率およ
びニュートラルな色調を合わせ持ち、かつ、単板で使用
しうる耐久性を有する熱線造幣ガ 〆ラスを提供するも
のである。The present invention provides a hot wire minting glass that has good hot wire minting performance, high visible light transmittance, and neutral color tone, and is durable enough to be used as a veneer.
［課題を解決するための手段］
本発明は、上記目的を達成するためになされたものであ
って、透明基体の上に被覆された第１層が、Ｔｉの窒化
物、Ｚｒの窒化物、Ｈｆの窒化物。[Means for Solving the Problems] The present invention has been made to achieve the above object, and the first layer coated on the transparent substrate is made of Ti nitride, Zr nitride, Nitride of Hf.
Ｃｒの窒化物の少な（ともひとつからなり、前記第１層
の上に被覆された第２層が二酸化チタンからなり、前記
第２層の上に被覆された第３層が１７以下の屈折率を有
する透明層である熱線造幣ガ・ラスである。The second layer coated on the first layer is made of titanium dioxide, and the third layer coated on the second layer has a refractive index of 17 or less. It is hot-wire minting glass, which is a transparent layer with a transparent layer.
本発明における最も大きな特徴は、熱線造幣性／能を有
する上記した金属の窒化物の層の上に、屈折率が大きい
二酸化チタン膜を被覆し、さらにその上に最外層として
屈折率が１．８以下の透明層を被覆したことである。最
外層の透明層の屈折率は１．８以下であることが必要で
、屈折率が１．８を越えると熱線造幣ガラスの色調をニ
ュートラルにす／ることができない。ここで二二一トラ
ルな色調とは、ｘｙ色度座標で表した熱線遮蔽ガラスと
用いたガラスとの色差△ｘ１ △ｙが、透過色の場合
ともに０．００５以下であり、反射色の場合△Ｘ、△ｙ
がともに０．０２以下であることをいう。The most significant feature of the present invention is that a titanium dioxide film having a high refractive index is coated on the above-mentioned metal nitride layer having hot wire minting properties/ability, and a titanium dioxide film having a high refractive index is further formed as the outermost layer. This means that a transparent layer of 8 or less is coated. The refractive index of the outermost transparent layer must be 1.8 or less; if the refractive index exceeds 1.8, the color tone of the hot-wire minted glass cannot be made neutral. Here, a neutral color tone means that the color difference △x1 △y between the heat ray shielding glass and the glass used, expressed in xy chromaticity coordinates, is 0.005 or less in the case of a transmitted color, and in the case of a reflective color. △X, △y
are both 0.02 or less.
上記した最外層の透明層になりうるものとしては、屈折
率が１．８以下であれば特に限定されないが、二酸化珪
素、酸化アルミニウム、シリコンドアルミニウムと酸素
とからなる化合物、シリコンとタンタルと酸素とからな
る化合物、シリコンとニオブと酸素とからなる化合物、
シリコンとアルミニウムと酸素と窒素からなる化合物が
、スクラッチや摩耗の如き機械的な外力にたいして強い
ので好ましい。とりわけ二酸化珪素は屈折率が１．４６
と小さいので、第二層の屈折率が２．２より太きい二酸
化チタン膜の上に積層して屈折率の差を大きくすること
ができ、優れた熱線造幣性能とニュ 。Materials that can be used as the outermost transparent layer are not particularly limited as long as the refractive index is 1.8 or less, but include silicon dioxide, aluminum oxide, a compound consisting of silicone aluminum and oxygen, silicon, tantalum, and oxygen. A compound consisting of silicon, niobium and oxygen,
A compound consisting of silicon, aluminum, oxygen, and nitrogen is preferred because it is resistant to external mechanical forces such as scratches and abrasion. In particular, silicon dioxide has a refractive index of 1.46.
Because of its small refractive index, it is possible to increase the difference in refractive index by laminating it on top of the second layer titanium dioxide film, which has a refractive index thicker than 2.2, resulting in excellent hot wire minting performance and new properties.
−トラルな色調が得られるので好ましい。被膜の酸やア
ルカリなどの対する化学的安定性を充分確保するうえか
らは、シリコンとタンタルと酸素との化合物の膜あるい
はシリコンとニオブと酸素との化合物の膜が好ましい。- It is preferable because a neutral color tone can be obtained. In order to ensure sufficient chemical stability of the film against acids, alkalis, etc., a film of a compound of silicon, tantalum, and oxygen or a film of a compound of silicon, niobium, and oxygen is preferable.
また、膜を被覆する時）生産の安定性からは、シリコン
とアルミニウムと酸素とからなる化合物またはシリコン
とアルミニウムと酸素と窒素とからなる化合物の膜が好
ましい。本発明の最外層の透明層は、必ずしも完全に透
明である必要はなく、光を吸収する原因となる酸素欠損
が被膜の透明性を大きく損なわない程度にあってもよい
。Furthermore, in terms of production stability (when coating a film), a film of a compound consisting of silicon, aluminum, and oxygen or a compound consisting of silicon, aluminum, oxygen, and nitrogen is preferred. The outermost transparent layer of the present invention does not necessarily have to be completely transparent, and may have oxygen vacancies that cause light absorption to an extent that does not significantly impair the transparency of the coating.
熱線造幣性能を大きくするためには、第１層の〆金属窒
化物の厚みは厚い方が好ましく、可視光線透過率を高く
するためには薄いほうが好ましい。In order to increase the hot wire minting performance, the thickness of the first layer of the final metal nitride is preferably thicker, and in order to increase the visible light transmittance, it is preferably thinner.
本発明においては、金属窒化物の厚みは、第２層の二酸
化チタンの厚みと第３層の透明層の厚みと組み合わせて
考慮され、熱線造幣性能を低下させ／ず、かつ、可視光
線透過率が７０％以上になるように定められる。とりわ
け、自動車用の窓ガラスとして好適に用いるには、金属
窒化物の厚みは、２〜１５ｎｍが好ましく、３〜１０ｎ
ｍが最も好ましい。In the present invention, the thickness of the metal nitride is considered in combination with the thickness of titanium dioxide in the second layer and the thickness of the transparent layer in the third layer, so that the thickness of the metal nitride is taken into consideration in combination with the thickness of the titanium dioxide layer as the second layer and the thickness of the transparent layer as the third layer. is set to be 70% or more. In particular, in order to suitably use it as a window glass for an automobile, the thickness of the metal nitride is preferably 2 to 15 nm, and 3 to 10 nm.
m is most preferred.
また、基体と第１層の金属窒化物膜との間の付着力を向
上させるために、屈折率が２〜２．５の透明層を光学特
性が大きく変化させない程度に、第１層と第２層の間に
設けることができる。たとえば、酸化錫、酸化チタン、
酸化タンタル、酸化ジルコニウムの膜を３０〜６０ｎｍ
の厚みで被覆することができる。In addition, in order to improve the adhesion between the substrate and the first layer metal nitride film, a transparent layer having a refractive index of 2 to 2.5 is formed between the first layer and the metal nitride film to the extent that the optical properties do not change significantly. It can be provided between two layers. For example, tin oxide, titanium oxide,
Tantalum oxide, zirconium oxide film with a thickness of 30 to 60 nm
It can be coated with a thickness of
本発明の熱線造幣ガラスの透明な基体としては、無色透
明なフロートガラス、ブロンズ、グレーグリーンなどの
色を有する熱線吸収フロートガラス（たとえば日本板硝
子曲製商品名ブロンズベーン、グレーベーンなど）を用
いることができる。As the transparent substrate of the heat-ray minted glass of the present invention, colorless transparent float glass, heat-absorbing float glass having a color such as bronze or gray-green (for example, Nippon Sheet Glass Co., Ltd. trade name Bronze Vane, Gray Vane, etc.) can be used. can.
とりわけ、ブロンズ色調のガラスを用いた場合は、ガラ
ス自体の色調を変化させず、かつ、自動車のボディの外
観とマツチして、良好な熱線造幣性能をもったガラスと
することができる。上記した透明層は、シリコン、アル
ミニウム、シリコンとアルミニウムの合金、シリコンと
タンタルの合金、シリコンとニオブの合金をターゲット
として直流反応性スパッタリング法で被覆することがで
きる。In particular, when bronze-toned glass is used, the glass does not change the color tone of the glass itself, matches the appearance of the car body, and has good hot-wire minting performance. The transparent layer described above can be coated by direct current reactive sputtering using silicon, aluminum, an alloy of silicon and aluminum, an alloy of silicon and tantalum, and an alloy of silicon and niobium as targets.
さらに公知の真空蒸着法やアーク蒸着法を用いることが
できる。同様に、金属の窒化物の層や二酸化チタンの層
についても、直流反応性スパッタリングや真空蒸着法、
アーク蒸着法を用いることができる。Further, known vacuum evaporation methods and arc evaporation methods can be used. Similarly, metal nitride layers and titanium dioxide layers can be formed using direct current reactive sputtering, vacuum evaporation,
Arc evaporation methods can be used.
［作用］
本発明によれば、透明な基体の上に被覆された第１層の
熱線造幣性能を有する膜は、第２層の高／屈折率の二酸
化チタンの膜と組み合わされて、光学干渉作用により大
きな熱線造幣性能を発揮する。〆さらに第２層の上に最
上層として屈折率が１．８以下の透明な層が被覆される
ことにより、可視光線透過率を低下させることなく、透
過色や反射色が目だたないニュートラルな色調のガラス
が得られる。また、本発明の最上層の膜は熱線遮蔽機能
を有する第１および第２の層を保護する。[Function] According to the present invention, the first layer of a film with thermal minting performance coated on a transparent substrate is combined with the second layer of high/refractive index titanium dioxide film to provide optical interference. Due to its action, it exhibits great hot wire minting performance. Furthermore, by coating the second layer with a transparent layer with a refractive index of 1.8 or less as the top layer, the visible light transmittance is not reduced and the transmitted color and reflected color are inconspicuous and neutral. A glass with a unique color tone can be obtained. Further, the top layer film of the present invention protects the first and second layers having a heat ray shielding function.
［実施例］
本発明を以下に実施例に基づいて説明する。第１図は、
本発明の熱線遮蔽ガラスの一部断面図で、ガラス１の上
に金属窒化物の層２が被覆され、その上に順次、二酸化
チタンの層３と屈折率が１．８以下の透明な層４が被覆
されている。[Examples] The present invention will be described below based on Examples. Figure 1 shows
This is a partial cross-sectional view of the heat-shielding glass of the present invention, in which a metal nitride layer 2 is coated on a glass 1, and a layer 3 of titanium dioxide and a transparent layer with a refractive index of 1.8 or less are sequentially formed on top of the metal nitride layer 2. 4 is coated.
実施例１
マグネトロンスパッタ装置内にターゲットとして金属チ
タンと石英ガラスとをセットした。洗浄した４ｍｍの厚
みのブロンズ色の熱線吸収フロートガラスをスパッタ装
置の真空槽内にいれ、真空ポンプで槽内の圧力を０．０
０４ Ｐ ａ以下にした。Example 1 Metallic titanium and quartz glass were set as targets in a magnetron sputtering device. Place the cleaned bronze-colored heat-absorbing float glass with a thickness of 4 mm into the vacuum chamber of the sputtering device, and reduce the pressure inside the chamber to 0.0 using a vacuum pump.
04 Pa or less.
それからアルゴン９４％窒素６％の混合ガスを槽内に導
入して、圧力を０．０４ Ｐ ａに調整した。金属チタ
ンターゲットに３Ａの電流を投入して、所定時間スパッ
タをすることにより、６ｎｍのＴ＋の窒化物の膜を形成
しスパッタを終了した。つぎに真空槽内にアルゴン４０
％酸素６０％からなる混合ガスを導入し、圧力を０．０
４Ｐａに調整した。Then, a mixed gas of 94% argon and 6% nitrogen was introduced into the tank, and the pressure was adjusted to 0.04 Pa. A current of 3 A was applied to the metal titanium target and sputtering was performed for a predetermined period of time to form a 6 nm T+ nitride film, and the sputtering was completed. Next, put 40 argon in the vacuum chamber.
A mixed gas consisting of 60% oxygen is introduced and the pressure is reduced to 0.0.
It was adjusted to 4Pa.
金属チタンのターゲ７）に８Ａの電流を投入して、所定
時間スパッタすることにより＋ １１０１ｎの厚みの
二酸化チタンの膜をＴ１の窒化物の膜の上に被覆しスパ
ッタを終了した。最後に真空槽内にアルゴン８０％酸素
２０％からなる混合ガスを導入し、圧力を０．０４Ｐａ
に調整した。石英ガラスのターゲットに３ＫＷの高周波
電力を投入して所定の時間スパッタすることにより、９
３ｎｍの二酸化珪素の膜を形成し、スパッタを終了した
。得られたサンプルｌの光学特性を第１表に示す。第１
表から、サンプルｌは可視光線をよく透過し、日射透過
率をよ（遮蔽することが分かる。A current of 8 A was applied to the metallic titanium target 7) and sputtering was performed for a predetermined period of time to coat the nitride film of T1 with a titanium dioxide film having a thickness of +1101 nm, and the sputtering was completed. Finally, a mixed gas consisting of 80% argon and 20% oxygen was introduced into the vacuum chamber, and the pressure was set to 0.04 Pa.
Adjusted to. By applying 3KW of high frequency power to a quartz glass target and sputtering for a predetermined time, 9
A 3 nm silicon dioxide film was formed and sputtering was completed. Table 1 shows the optical properties of the sample I obtained. 1st
From the table, it can be seen that sample 1 transmits visible light well and blocks solar transmittance well.
また、得られたサンプル１と用いたブロンズの熱線吸収
ガラス自身との色差をｘｙ色度座標により評価したとこ
ろ、透過色においてはＸの色差△Ｘは０．０００５、ｙ
の色差Δｙは０．００１９と小さな値が得られた。ガラ
ス側から光が入射するときの反射色の差は、ΔＸは０．
００５６、△ｙは０００１７であり、ガラス面とは直角
の方向から３０°傾斜した方向から見たときの反射色の
差についても△Ｘがｏ、ｏ ｏ ａ ｏ、△ｙが０．０
０５０と極めて小さい色差であった。サンプルｌと用い
たガラスとの外観色調の差はほとんど認められなかった
０
第１層の金属の窒化物の種類と厚み、第２層の二酸化チ
タンの厚み、第３層の屈折率が１８以下の透明層の物質
と厚みを変えて、サンプルｌと同じようにして熱線遮蔽
ガラスのサンプル２〜７を得た。サンプルを作成するに
あたり、第１層の金属の窒化物の膜は、金属をターゲッ
トとしてアルゴンと窒素の混合ガスによる反応性スパッ
タにより被覆し、第３層の透明層は、それぞれアルミニ
ウムシリサイド、タンタルシリサイド、ニホウ化ジルコ
ニウムをターゲットとしてアルゴンと酸素の混合ガス、
あるいはアルゴンと酸素と窒素の混合ガスによる反応性
スパッタにより被覆した。In addition, when the color difference between the obtained sample 1 and the bronze heat-absorbing glass used itself was evaluated using xy chromaticity coordinates, the color difference ΔX of X in the transmitted color was 0.0005, y
The color difference Δy was as small as 0.0019. The difference in reflected color when light enters from the glass side is ΔX is 0.
0056, △y is 00017, and △X is o, o o a o, △y is 0.0 regarding the difference in reflected color when viewed from a direction tilted 30 degrees from the direction perpendicular to the glass surface.
The color difference was extremely small at 0.050. There was almost no difference in appearance color tone between Sample 1 and the glass used.0 The type and thickness of the metal nitride in the first layer, the thickness of titanium dioxide in the second layer, and the refractive index of the third layer were 18 or less. Heat-shielding glass samples 2 to 7 were obtained in the same manner as sample 1, except that the material and thickness of the transparent layer were changed. To prepare the sample, the first layer of metal nitride film was coated by reactive sputtering using a mixed gas of argon and nitrogen using metal as a target, and the third transparent layer was coated with aluminum silicide and tantalum silicide, respectively. , a mixed gas of argon and oxygen targeting zirconium diboride,
Alternatively, the coating was performed by reactive sputtering using a mixed gas of argon, oxygen, and nitrogen.
各サンプルの熱線遮蔽膜の膜構成と得られたサンプルの
可視光線透過率と日ｆＮＸ！！ｉ過率を、第１表にまと
めて示す。サンプル２〜７は、いずれも可視光線透過率
が７０％以上と高（、日射透過率が６０％以下で、良好
な太陽光線エネルギに対する遮蔽性を有することがわか
る。またサンプル２〜７は、いずれもサンプル鳳と同じ
ように、用いたガラスとの色差は、はとんど感じられな
かった。The film composition of the heat ray shielding film of each sample, the visible light transmittance of the obtained sample, and the fNX! ! The i pass rates are summarized in Table 1. Samples 2 to 7 all have a high visible light transmittance of 70% or more (and a solar transmittance of 60% or less, indicating that they have good shielding properties against solar energy. Also, samples 2 to 7 have a high visible light transmittance of 70% or more). In both cases, like the sample Otori, there was almost no discernible difference in color from the glass used.
比較例
実施例に用いたスパッタ装置により、４ｍｍの厚みのブ
ロンズの熱線吸収フロートガラスに第１の二酸化チタン
膜、チタンの窒化物（ＴＩＮ）膜、第２の二酸化チタン
膜を順次被覆した。それぞれの膜の厚みは、用いたガラ
スとの色差が小さくなるように選び、第１の二酸化チタ
ンの厚みを２７ｎｍ、チタンの窒化物の厚みを７ｎｍ、
第２の二酸化チタンの厚みを７６ｎｍとした。得ら
れた比較サンプルの光学特性を測定したところ、可視光
線透過率７０．５％、日射透過率５６．１％であった。Comparative Example Using the sputtering apparatus used in the example, a 4 mm thick bronze heat-absorbing float glass was sequentially coated with a first titanium dioxide film, a titanium nitride (TIN) film, and a second titanium dioxide film. The thickness of each film was selected so that the color difference with the glass used was small, and the thickness of the first titanium dioxide was 27 nm, the thickness of the titanium nitride was 7 nm, and the thickness of the first titanium dioxide was 27 nm.
The thickness of the second titanium dioxide was 76 nm. When the optical properties of the obtained comparative sample were measured, the visible light transmittance was 70.5% and the solar transmittance was 56.1%.
しかし、用いたガラスとの透過光による色差は、△Ｘが
０．００９１．△ｙが０．００１１、反射光による色差
は、ΔＸが０．０５６２、△ｙが０００２４であり、透
過色、反射色とも赤紫色を呈していた。と（に反射の色
差は、斜めからサンプルを見たときに大きかった。However, the color difference due to transmitted light with the glass used is ΔX of 0.0091. Δy was 0.0011, and the color difference due to reflected light was ΔX of 0.0562 and Δy of 00024, and both the transmitted color and the reflected color were reddish-purple. The color difference in reflection was greater when the sample was viewed from an angle.
以上述べたように、本発明にかかるサンプル１〜７は、
用いるガラスとは色調が異ならない外観をし、かつ、７
０％以上の可視光線透過率と６０％以下の日射透過率で
表される良好な熱線遮蔽性を有していることが分かる。As mentioned above, samples 1 to 7 according to the present invention are
It has an appearance that does not differ in color from the glass used, and
It can be seen that it has good heat ray shielding properties as expressed by visible light transmittance of 0% or more and solar radiation transmittance of 60% or less.
［発明の効果］
本発明の熱線遮蔽ガラスは、太陽光線に対する良好な熱
線遮蔽性能を有し、透過光および反射光による色調は用
いるガラスとの差が小さ（なっていて、ギラギラした外
観を呈することがないので、自動車の窓ガラスに用いる
ときは、車体や内装材との色彩の調和を損ねることなく
、室内の冷房負荷を低減することができる。また、本発
明の熱線遮蔽ガラスは可視光線透過率が高いので、車外
の物体に対する視認性が確保できる。また、被膜の最上
層の保護膜は、スクラッチや摩耗のような機械的な外力
に対して耐久性があるので単板で用いることができる。[Effects of the Invention] The heat ray shielding glass of the present invention has good heat ray shielding performance against sunlight, and the color tone due to transmitted light and reflected light has a small difference from that of the glass used, giving it a glare appearance. Therefore, when used for automobile window glass, it is possible to reduce the indoor cooling load without impairing the color harmony with the car body and interior materials.In addition, the heat ray shielding glass of the present invention can reduce visible light rays. The high transmittance ensures visibility to objects outside the vehicle.Also, the top layer of the coating is durable against mechanical external forces such as scratches and abrasion, so it can be used as a single plate. I can do it.
したがって自動車のｆｌｆｆｉを増加させることな（、
車内の冷房の負荷を低減することができる。Therefore, without increasing the flfffi of the car (,
The load on air conditioning inside the vehicle can be reduced.
第１図は、本発明の熱線遮蔽ガラスの一部断面図である
。
ｌ・・・透明基体、２・・・金属窒化物の層、３・・・
二酸化チタンの層、４・・・１．８以下の屈折率を有す
る透明層
第１図
！、事件の表示
特願平２−７４１９０号
２、発明の名称
熱線造幣ガラス
３、補正をする者
事件との関係 特許出願人
住所 大阪府大阪市中央区道修町３丁目５番１１号名
称（４００）日本板硝子株式会社
代表者 中島違二
４、代理人
住所 東京都港区新橋５丁目１１番３号新橋住友ビル
日本板硝子株式会社 特許部内
６、補正の対象
、補正の内容
）願書の発明の名称の欄
別紙の通りに訂正する。
）明細書の発明の詳細な説明の欄
（１）明細書の第２頁の第１３行、第１５行、第１８行
、第７１９行の「造幣」をそれぞれ「遮蔽」に訂正する
。
（２）明細書の第３頁の第４行、第１Ｏ行、第１５行、
第２０行の「造幣」をそれぞれ「遮蔽」に訂正する。
（
では、良好な熱線遮蔽ガラス）に訂正する。
（４）明細書の第４頁の第６行、第８行、第１７行、第
１９行の「造幣」をそれぞれ「遮蔽」に訂正する。
（５）明細書の第４頁の第１６行から第１７行の「１７
」をｒｌ、８Ｊに訂正する。
（６）明細書の第５頁の第５行の「造幣」を１！！蔽」
に訂正する。
７）明細書の第６頁の第２行、第１５行、第２０行のｒ
ｌ幣」をそれぞれ「遮蔽」に訂正する。
８）明細書の第７頁の第１３行、第２０行の「造幣Ｊを
それぞれ「遮蔽」に訂正する。
９）明細書の第８頁の第１３行、第１５行の「造幣」を
それぞれ「遮蔽」に訂正する。FIG. 1 is a partial cross-sectional view of the heat ray shielding glass of the present invention. l...Transparent substrate, 2...Metal nitride layer, 3...
A layer of titanium dioxide, 4...a transparent layer with a refractive index of less than 1.8 Figure 1! , Indication of the case Japanese Patent Application No. 2-74190 2, Name of the invention Hot ray minting glass 3, Person making the amendment Relationship to the case Patent applicant address 3-5-11 Doshomachi, Chuo-ku, Osaka-shi, Osaka Name (400 ) Nippon Sheet Glass Co., Ltd. Representative: Iji Nakajima 4, Agent address: Shinbashi Sumitomo Building, 5-11-3 Shinbashi, Minato-ku, Tokyo Japan Patent Department 6, Subject of amendment, Contents of amendment) Name of the invention in the application Correct the column as shown in the attached sheet. ) Column for detailed description of the invention in the specification (1) Correct "minting" to "shielding" in lines 13, 15, 18, and 719 on page 2 of the specification. (2) Line 4, line 1O, line 15 on page 3 of the specification,
Correct "mint" in line 20 to "shield". (Corrected to ``good heat shielding glass''). (4) "Minting" in lines 6, 8, 17, and 19 on page 4 of the specification is corrected to "shielding." (5) “17” from line 16 to line 17 on page 4 of the specification
" is corrected to rl, 8J. (6) “Minute” in the 5th line of the 5th page of the specification is 1! ! "cover"
Correct. 7) r on page 6, line 2, line 15, and line 20 of the specification
Correct each word ``l note'' to ``shield.'' 8) Correct "Minute J" in lines 13 and 20 on page 7 of the specification to "shield" respectively. 9) Correct "Minute" in lines 13 and 15 on page 8 of the specification to "shield" respectively.
Claims (4)
ｒの窒化物、Ｈｆの窒化物、Ｃｒの窒化物の少なくとも
ひとつが被覆され、前記第１層の上に第２層として二酸
化チタンが被覆され、前記第２層の上に第３層として１
．８以下の屈折率を有する透明層が被覆された熱線遮蔽
ガラス。(1) Ti nitride, Z
At least one of r nitride, Hf nitride, and Cr nitride is coated, titanium dioxide is coated as a second layer on the first layer, and titanium dioxide is coated as a third layer on the second layer.
．． Heat-shielding glass coated with a transparent layer having a refractive index of 8 or less.
みが９０〜１１０ｎｍであり、前記第３層の厚みが８０
〜１１０ｎｍであることを特徴とする特許請求の範囲の
第１項に記載の熱線遮蔽ガラス。(2) The thickness of the first layer is 2 to 15 nm, the thickness of the second layer is 90 to 110 nm, and the thickness of the third layer is 80 nm.
The heat ray-shielding glass according to claim 1, characterized in that the wavelength is 110 nm to 110 nm.
シリコンとアルミニウムと酸素とからなる化合物、シリ
コンとタンタルと酸素とからなる化合物、シリコンとニ
オブと酸素とからなる化合物、シリコンとアルミニウム
と酸素と窒素とからなる化合物、ジルコニウムとボロン
と酸素とからなる化合物のいずれかであることを特徴と
する特許請求の範囲の第１項または第２項に記載の熱線
遮蔽ガラス。(3) The transparent layer is made of silicon dioxide, aluminum oxide,
A compound consisting of silicon, aluminum and oxygen, a compound consisting of silicon, tantalum and oxygen, a compound consisting of silicon, niobium and oxygen, a compound consisting of silicon, aluminum, oxygen and nitrogen, a compound consisting of zirconium, boron and oxygen The heat ray shielding glass according to claim 1 or 2, which is any one of the compounds.
％以下となるように、第１、第２および第３層の厚みが
それぞれ調整されたことを特徴とする特許請求の範囲の
第１項ないし第３項のいずれかの項に記載の熱線遮蔽ガ
ラス。(4) Visible light transmittance is 70% or more, solar transmittance is 60%
The heat ray shielding according to any one of claims 1 to 3, wherein the thicknesses of the first, second, and third layers are each adjusted so that glass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7419090A JP2811885B2 (en) | 1990-03-23 | 1990-03-23 | Heat shielding glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7419090A JP2811885B2 (en) | 1990-03-23 | 1990-03-23 | Heat shielding glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03275533A true JPH03275533A (en) | 1991-12-06 |
| JP2811885B2 JP2811885B2 (en) | 1998-10-15 |
Family
ID=13540005
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7419090A Expired - Lifetime JP2811885B2 (en) | 1990-03-23 | 1990-03-23 | Heat shielding glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2811885B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0650938A1 (en) * | 1993-11-02 | 1995-05-03 | Saint-Gobain Vitrage | Transparent substrate coated with a metallic nitride layer |
| FR2766817A1 (en) * | 1997-07-31 | 1999-02-05 | Saint Gobain Vitrage | TRANSPARENT SUBSTRATE WITH AT LEAST ONE REFLECTIVE LAYER AND METHOD OF OBTAINING THE SAME |
| EP1110920A1 (en) * | 1999-12-22 | 2001-06-27 | Sony Corporation | LIght-absorptive antireflection filter, display device, and methods of producing the same |
| WO2001085636A1 (en) * | 2000-05-09 | 2001-11-15 | Central Glass Company, Limited | Vehicle-use low-reflection glass |
| JP2013535403A (en) * | 2010-08-10 | 2013-09-12 | サン−ゴバン グラス フランス | Glass panel with solar shading properties |
| JP2018525629A (en) * | 2015-08-05 | 2018-09-06 | エフ．ホフマン−ラ ロシュ アーゲーＦ． Ｈｏｆｆｍａｎｎ−Ｌａ Ｒｏｃｈｅ Ａｋｔｉｅｎｇｅｓｅｌｌｓｃｈａｆｔ | Use of titanium nitride as an electrode in non-Faraday electrochemical cells |
-
1990
- 1990-03-23 JP JP7419090A patent/JP2811885B2/en not_active Expired - Lifetime
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0650938A1 (en) * | 1993-11-02 | 1995-05-03 | Saint-Gobain Vitrage | Transparent substrate coated with a metallic nitride layer |
| FR2711983A1 (en) * | 1993-11-02 | 1995-05-12 | Saint Gobain Vitrage | Transparent substrate provided with a layer of metal nitride. |
| FR2766817A1 (en) * | 1997-07-31 | 1999-02-05 | Saint Gobain Vitrage | TRANSPARENT SUBSTRATE WITH AT LEAST ONE REFLECTIVE LAYER AND METHOD OF OBTAINING THE SAME |
| WO1999006335A1 (en) * | 1997-07-31 | 1999-02-11 | Saint Gobain Vitrage | Transparent substrate provided with at least one reflecting coating and method for obtaining same |
| EP1110920A1 (en) * | 1999-12-22 | 2001-06-27 | Sony Corporation | LIght-absorptive antireflection filter, display device, and methods of producing the same |
| WO2001085636A1 (en) * | 2000-05-09 | 2001-11-15 | Central Glass Company, Limited | Vehicle-use low-reflection glass |
| JP2001322833A (en) * | 2000-05-09 | 2001-11-20 | Central Glass Co Ltd | Low-reflection glass for vehicle |
| JP2013535403A (en) * | 2010-08-10 | 2013-09-12 | サン−ゴバン グラス フランス | Glass panel with solar shading properties |
| JP2018525629A (en) * | 2015-08-05 | 2018-09-06 | エフ．ホフマン−ラ ロシュ アーゲーＦ． Ｈｏｆｆｍａｎｎ−Ｌａ Ｒｏｃｈｅ Ａｋｔｉｅｎｇｅｓｅｌｌｓｃｈａｆｔ | Use of titanium nitride as an electrode in non-Faraday electrochemical cells |
| US11098354B2 (en) | 2015-08-05 | 2021-08-24 | Roche Sequencing Solutions, Inc. | Use of titanium nitride as an electrode in non-faradaic electrochemical cell |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2811885B2 (en) | 1998-10-15 |
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| JPH01208344A (en) | Transparent plate with gold reflected color | |
| JPH03122034A (en) | Heat radiation reflecting laminated sheet |