JPH0460061B2 - - Google Patents
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- Publication number
- JPH0460061B2 JPH0460061B2 JP62018579A JP1857987A JPH0460061B2 JP H0460061 B2 JPH0460061 B2 JP H0460061B2 JP 62018579 A JP62018579 A JP 62018579A JP 1857987 A JP1857987 A JP 1857987A JP H0460061 B2 JPH0460061 B2 JP H0460061B2
- Authority
- JP
- Japan
- Prior art keywords
- layer
- thickness
- tio
- tinx
- 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.)
- Expired - Lifetime
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- 239000011521 glass Substances 0.000 claims description 42
- 239000000758 substrate Substances 0.000 claims description 26
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 25
- 229910010421 TiNx Inorganic materials 0.000 claims description 24
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 238000004544 sputter deposition Methods 0.000 claims description 14
- 238000002834 transmittance Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000005240 physical vapour deposition Methods 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- 238000001429 visible spectrum Methods 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 80
- 229910010413 TiO 2 Inorganic materials 0.000 description 21
- 235000019646 color tone Nutrition 0.000 description 19
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 230000003595 spectral effect Effects 0.000 description 11
- 239000007789 gas Substances 0.000 description 9
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000011241 protective layer Substances 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 239000003086 colorant Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000005546 reactive sputtering Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001009 interstitial alloy Inorganic materials 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 238000001659 ion-beam spectroscopy Methods 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000005340 laminated glass Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Landscapes
- Surface Treatment Of Glass (AREA)
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、ガラス基板上にスパツタリング法等
の物理蒸着法によつて、可視スペクトル帯域で40
％以下の透過率及び多種の反射色調を有する熱線
反射ガラスを製造する方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a method for depositing 40% in the visible spectrum band on a glass substrate by a physical vapor deposition method such as a sputtering method.
% or less and a variety of reflective colors.
［従来の技術］
可視スペクトル帯域で低い透過率を有する膜
は、太陽光スペクトルもその大部分を遮断し、特
に大陸的気候即ち、極端に暑い夏の地域に使用さ
れ、ソーラーコントロールパネルと称される。[Prior Art] Membranes with low transmittance in the visible spectral band also block a large part of the solar spectrum and are used especially in continental climates, i.e. regions with extremely hot summers, and are called solar control panels. Ru.
このようなソーラーコントロールパネルの代表
的膜材料としては、CrやTiなどの遷移金属の純
金属層が知られている。（特公昭47−14594、特開
昭60−42253）。しかし、これらの金属層は、その
反射色調が中性色であり、色調に変化が乏しい。 Pure metal layers of transition metals such as Cr and Ti are known as typical film materials for such solar control panels. (Special Publication No. 47-14594, Japanese Patent Publication No. 60-42253). However, the reflected color tone of these metal layers is neutral, and there is little change in color tone.
独特の反射色調を呈する固有の有効層として
は、金、銀、銅などの貴金属があり、しかもこれ
らの貴金属は、赤外域における反射を非常に高く
熱反特性も優れている事が公知である。しかしな
がら、これらの貴金属膜はガラス基板に対する付
着力が極めて弱く、又その耐候性を充分でない。
よつて、これらの貴金属膜は、通常付着層と保護
層の間に配置される。付着層としては、同様の光
学的性質を有し、例えばクロムのような金属又は
誘電体が使用される。保護層としては一般に誘電
材料が使用される。（特開昭54−120688、特開昭
50−39314）。この様な付着層及び保護層を用いる
事は、その干渉効果のために使用する貴金属に応
じて阻止する事がきわめて困難な強い色刺激を多
少によらず有する欠点があある。 Noble metals such as gold, silver, and copper are effective layers that exhibit unique reflective colors, and these precious metals are known to have extremely high reflection in the infrared region and excellent heat response properties. . However, these noble metal films have extremely weak adhesion to glass substrates and do not have sufficient weather resistance.
These noble metal films are therefore usually placed between the adhesion layer and the protective layer. As the adhesion layer, metals or dielectrics with similar optical properties, such as chromium, are used. Dielectric materials are generally used as protective layers. (JP-A-54-120688, JP-A-Showa
50−39314). The use of such adhesion and protective layers has the disadvantage that, due to their interference effects, they have more or less strong color irritation which, depending on the noble metal used, is very difficult to prevent.
一方、この貴金属層を誘電体層で挟んだ３層構
造の干渉効果を利用して逆に色調表現を多様化す
る方法がある。しかしながら、この様にして得ら
れる色調は一般に彩度が高く建築用として好まし
からざるものが多い。 On the other hand, there is a method of diversifying color tone expression by utilizing the interference effect of a three-layer structure in which a noble metal layer is sandwiched between dielectric layers. However, the color tones obtained in this manner generally have high chroma and are often undesirable for architectural use.
又、この様に付着層や保護層を備えた貴金属層
も、単板として使用するには、その耐久性が不充
分であるため、合せガラスとして使用したり、複
層化して使用したりする事が多い。 In addition, the durability of the noble metal layer with an adhesion layer and protective layer is insufficient to be used as a single glass, so it is used as a laminated glass or as a multi-layered glass. There are many things.
さらに、金属層を使用しないで、半導体材料の
単層を用いる事も公知となつている。この様な半
導体材料としてインジウム−スズ酸化物があり、
赤外域の反射特性も優れているが、その透過率が
70％より高く、又その色調を所望に応じて変化す
る事ができない。 Furthermore, it is also known to use a single layer of semiconductor material without using a metal layer. Indium-tin oxide is an example of such a semiconductor material.
The reflection characteristics in the infrared region are also excellent, but the transmittance is
higher than 70%, and the color tone cannot be changed as desired.
一方、同じ半導体材料である窒化チタンは高い
硬度を有し、化学的耐久性も優れている。又その
電気抵抗も比較的低いために、通常の金属膜以上
の赤外域反射特性を有する。その色調も光沢のあ
る黄金色を呈し、この特性を利用して、銅等の金
属表面に被覆することで、超硬材料、装飾物等に
も利用される。しかし、窒化チタンが黄金色を呈
するには、1000Å以上の膜厚が必要であり、その
結果透過率が極端に低くなり、建築用としては好
ましくない。又、インジウム−スズ酸化物と同様
にその色調を所望に応じて変化する事ができな
い。 On the other hand, titanium nitride, which is also a semiconductor material, has high hardness and excellent chemical durability. Also, since its electrical resistance is relatively low, it has infrared reflection characteristics better than ordinary metal films. Its color is a shiny golden yellow, and by utilizing this property, it can be used for ultra-hard materials, decorations, etc. by coating metal surfaces such as copper. However, in order for titanium nitride to exhibit a golden color, a film thickness of 1000 Å or more is required, resulting in extremely low transmittance, making it undesirable for architectural use. Also, like indium-tin oxide, its color tone cannot be changed as desired.
さらに窒化チタン膜は優れた化学的耐久性を示
すが、この特性を持つ窒化チタン膜を通常のスパ
ツタリングで作製するには、高い基板温度（400
℃〜500℃）が必要であり、この様に基板を加熱
する事は装置のハードの面で不利である。 In addition, titanium nitride films exhibit excellent chemical durability, but in order to fabricate titanium nitride films with this property by conventional sputtering, high substrate temperatures (400
℃ to 500℃), and heating the substrate in this way is disadvantageous in terms of equipment hardware.
窒化チタンは金属であるチタン原子のマトリツ
クス中に窒素原子が侵入した侵入型化合物であ
り、このため、金属と窒化チタンの密着性は比較
的良好である。 Titanium nitride is an interstitial compound in which nitrogen atoms have entered a matrix of metal titanium atoms, and therefore the adhesion between the metal and titanium nitride is relatively good.
しかしながら、窒化チタンはガラスとの密着性
が充分でなく、耐擦傷性に問題がある。又窒化チ
タン膜は、かなり内部応力が高い膜であるので、
この事実とガラスへの低密着性が相まつて、膜は
がれを起こす原因となる。このため、この窒化チ
タンが熱反膜としては、比較的優れた特性を持つ
ているのに、金属基材に対してしか利用できず、
ガラスに適用しにくいため実際に実用化される範
囲を狭ばめている。 However, titanium nitride does not have sufficient adhesion to glass and has a problem in scratch resistance. Also, titanium nitride film has a fairly high internal stress, so
This fact, combined with the low adhesion to glass, causes the film to peel off. For this reason, although titanium nitride has relatively excellent properties as a heat reaction film, it can only be used for metal substrates.
Because it is difficult to apply to glass, the scope of its practical use is narrowed.
［発明の解決しようとする問題点］
本発明は、従来技術が有していた前述の様な欠
点がなく、可視スペクトル帯域で40％以下の透過
率とブルー色やグリーン色などの反射色調を有す
る熱線反射ガラスを提供することを目的とする。[Problems to be Solved by the Invention] The present invention does not have the above-mentioned drawbacks of the prior art, and has a transmittance of 40% or less in the visible spectrum band and a reflection color tone such as blue or green. The object of the present invention is to provide a heat ray reflective glass having the following characteristics.
［問題点を解決するための手段］
本発明は、前述の問題点を解決すべくなされた
ものであり、ガラス基板上に第１層として酸素含
有雰囲気中で10Å〜200Åの厚さを有する酸化チ
タン（TiO2）層を物理蒸着法により形成し、次
いで前記第１層上に第２層として純窒素雰囲気中
で窒化チタン（TiNx，ｘ＞1.0）層をスパツタリ
ング法により形成し、更にその第２層上に第３層
として酸素含有雰囲気中で10Å〜200Åの厚さを
有する酸化チタン（TiO2）層を物理蒸着法によ
り形成することを特徴とする可視スペクトル帯域
で40％以下の透過率及び熱線に対する高い反射能
を有する熱線反射ガラスの製法を提供するもので
ある。[Means for Solving the Problems] The present invention was made to solve the above-mentioned problems, and consists of forming an oxide film having a thickness of 10 Å to 200 Å in an oxygen-containing atmosphere as a first layer on a glass substrate. A titanium (TiO 2 ) layer is formed by a physical vapor deposition method, and then a titanium nitride (TiNx, x>1.0) layer is formed as a second layer on the first layer by a sputtering method in a pure nitrogen atmosphere. A titanium oxide (TiO 2 ) layer having a thickness of 10 Å to 200 Å is formed as a third layer on the two layers by physical vapor deposition in an oxygen-containing atmosphere.It has a transmittance of 40% or less in the visible spectrum band. The present invention also provides a method for producing a heat ray reflective glass having high reflectivity against heat rays.
第１図は、本発明により得られた熱線反射ガラ
スの膜構成を示すための断面図を示す。図におい
て、１はガラス基板、２は第１層のTiO2層、３
は第２層のTiNx層（ｘ＞１）を示し、４は第３
層のTiO2層を示す。 FIG. 1 shows a cross-sectional view showing the film structure of the heat ray reflective glass obtained by the present invention. In the figure, 1 is a glass substrate, 2 is a first layer of TiO 2 , and 3 is a glass substrate.
indicates the second TiNx layer (x>1), and 4 indicates the third TiNx layer (x>1).
The layer TiO2 layer is shown.
本発明は、TiNx（ｘ＞1.0）層をTiO2層で挟ん
だ３層構造を基本構成とするもので、その膜厚構
成は要求している色調によつて異なる。 The basic structure of the present invention is a three-layer structure in which a TiNx (x>1.0) layer is sandwiched between two TiO layers, and the film thickness structure varies depending on the desired color tone.
ブルー色系のガラス基板側からの反射色調が必
要な場合は、第１層のTiO2層は10Å〜150Å、好
ましくは25Å〜125Å、特に50Å〜100Åに、第２
層のTiNx層は（ｘ＞1.0）は195Å〜375Å、好ま
しくは225Å〜345Å、特に255Å〜315Åに、第３
層のTiO2層は75Å〜225Å、好ましくは10Å〜
200Å、特に125Å〜175Åにする事が色差の値を
低く押さえるために望ましい。 If a blue-ish reflection color tone from the glass substrate side is required, the first TiO2 layer should have a thickness of 10 Å to 150 Å, preferably 25 Å to 125 Å, especially 50 Å to 100 Å, and the second
The TiNx layer (x > 1.0) is 195 Å to 375 Å, preferably 225 Å to 345 Å, especially 255 Å to 315 Å, with a third
The TiO2 layer of the layer is 75 Å ~ 225 Å, preferably 10 Å ~
It is desirable to set the thickness to 200 Å, especially 125 Å to 175 Å in order to keep the color difference value low.
又グリーン色系のガラス基板側からの反射色調
が必要な場合は、第１層のTiO2層は100Å〜200
Å、好ましくは120Å〜200Å、特に140Å〜180
Å、第２層のTiNx層（ｘ＞1.0）は325Å〜475
Å、好ましくは350Å〜450Å、特に375Å〜425Å
に、第３層のTiO2の層は15Å〜225Å、好ましく
は50Å〜190Å、特に85Å〜155Åにする事が、色
差の値を低く押されるために望ましい。 In addition, if a green color reflected from the glass substrate side is required, the first TiO2 layer should be 100 Å to 200 Å.
Å, preferably 120Å to 200Å, especially 140Å to 180Å
Å, the second TiNx layer (x>1.0) is 325 Å to 475
Å, preferably 350 Å to 450 Å, especially 375 Å to 425 Å
In addition, it is desirable that the third TiO 2 layer has a thickness of 15 Å to 225 Å, preferably 50 Å to 190 Å, particularly 85 Å to 155 Å, in order to keep the color difference value low.
又グリーン色系のガラス基板側からの反射色調
を与える別の系としては、第１層のTiO2層は50
Å〜170Å、好ましくは70Å〜150Å、特に90Å〜
130Å、第２層のTiNx層（ｘ＞1.0）は340Å〜
460Å、好ましくは360Å〜440Å、特に380Å〜
420Å、第３層のTiO2層は、105Å〜225Å、好ま
しくは130Å〜230Å、特に155Å〜200Åにする事
が、同様に色差の値を低く押さえるために望まし
い。 In addition, as another system that gives a green color tone reflected from the glass substrate side, the first TiO 2 layer is 50%
Å ~ 170 Å, preferably 70 Å ~ 150 Å, especially 90 Å ~
130 Å, second layer TiNx layer (x>1.0) 340 Å ~
460 Å, preferably 360 Å to 440 Å, especially 380 Å to
420 Å, and the third TiO2 layer has a thickness of 105 Å to 225 Å, preferably 130 Å to 230 Å, particularly 155 Å to 200 Å, in order to similarly keep the color difference value low.
本発明において、TiO2層を形成する方法とし
ては、スパツタリング法、真空蒸着法、イオンプ
レーテイング法などの物理蒸着法が採用され、
又、TiNx層（ｘ＞１）を形成する方法として
は、スパツタリング法、が採用される。 In the present invention, a physical vapor deposition method such as a sputtering method, a vacuum evaporation method, or an ion plating method is adopted as a method for forming the TiO2 layer.
Furthermore, a sputtering method is employed as a method for forming the TiNx layer (x>1).
特に、本発明に使用するTiO2層、TiNx層（ｘ
＞１）はすべて通常の反応スパツタリング法、例
えば、陰極反応スパツタリング法、高周波スパツ
タリング法、イオンビームスパツタリング法など
において、Ti金属をターゲツトとし、雰囲気ガ
スを変えるだけで作成可能であるという製造プロ
セス上有利な点を有する。 In particular, the TiO 2 layer and TiNx layer (x
> 1) are all due to the production process, which can be created by using Ti metal as a target and simply changing the atmospheric gas in normal reactive sputtering methods, such as cathode reactive sputtering method, radio frequency sputtering method, ion beam sputtering method, etc. has advantages.
TiO2層を作成する際には、雰囲気ガスとして
主に酸素ガスを用いる。又、この時、Arガスを
添加しても良い。（Ar＋O2）の混合ガスを用いる
とTiO2の製膜速度が早くなる。 When creating the TiO 2 layer, oxygen gas is mainly used as the atmospheric gas. Also, at this time, Ar gas may be added. When a mixed gas of (Ar+O 2 ) is used, the TiO 2 film forming speed becomes faster.
又、TiNx層（ｘ＞1.0）を作成する際には、雰
囲気ガスとして 100％の窒素ガスを用いる。 Furthermore, when creating the TiNx layer (x>1.0), 100% nitrogen gas is used as the atmospheric gas.
本発明の３層の構成膜を作成する際には、基板
温度を上げる必要はなく室温で行なう事ができ
る。 When forming the three-layer constituent film of the present invention, there is no need to raise the substrate temperature, and the process can be carried out at room temperature.
［作用］
本発明において、ブルー色、グリーン色、など
の色調表現はTiO2層、TiNx層、の相互の干渉効
果を利用している。しかしながら、使用している
TiO2層の厚みが比較的薄いために、製膜制御の
面で有利である。例えば、ガラス基板側からの反
射色調としてグリーン反射を与える構成として、
第１層としてTiO2層（厚み1080Å）、第２層とし
てTiNx層（厚み390Å）（ｘ＞1.0）、第３層とし
てTiO2層（厚み265Å）という構成が存在する
が、この構成では全体の膜厚が厚く製膜に時間が
かかる。特にTiO2膜は製膜速度が遅く、コスト
面でも不利な条件になる。又本発明を建築用とし
て用いる際には、大面積における均一性や、大量
生産を行なう場合の再現性が重要な因子である。
これらの因子において色の違い、即ち色差の値を
２以下に押さえるためには、本発明のグリーン色
反射色調系では、各層の膜厚の変動を±５％にす
るだけで充分である。この±５％という値は通常
のスパツタ装置において特別な措置を講じなくて
も達成可能である。一方、比較のためにここであ
げた全体の膜厚が厚いグリーン色反射色調系で
は、色差の値を２以下に押さえるためには膜厚の
変動を±２％以下に制御しなげればならない層が
ある。この±２％という値は、何か特別の手段を
講じる事が必要であり、また高価なモニター設備
が必要となる。[Function] In the present invention, color tones such as blue and green are expressed using the mutual interference effect between the two TiO layers and the TiNx layer. However, using
Since the thickness of the TiO 2 layer is relatively thin, it is advantageous in terms of film formation control. For example, as a configuration that gives green reflection as a reflection color from the glass substrate side,
There is a configuration in which the first layer is 2 TiO layers (thickness 1080 Å), the second layer is a TiNx layer (thickness 390 Å) (x>1.0), and the third layer is 2 TiO layers (thickness 265 Å). The film is thick and takes time to form. In particular, the TiO 2 film has a slow film formation speed and is disadvantageous in terms of cost. Further, when the present invention is used for construction purposes, uniformity over a large area and reproducibility in mass production are important factors.
In order to suppress the color difference in these factors, that is, the color difference value, to 2 or less, in the green reflective color tone system of the present invention, it is sufficient to make the variation in the film thickness of each layer within ±5%. This value of ±5% can be achieved in ordinary sputtering equipment without special measures. On the other hand, in the green reflective color tone system with a thick overall film thickness, as shown here for comparison, in order to keep the color difference value to 2 or less, the variation in film thickness must be controlled to less than ±2%. There are layers. This value of ±2% requires some special measures and requires expensive monitoring equipment.
本発明によつて得られる反射色調は、淡色調的
のものが多いが、色刺激が少ないため、建築用な
どには好ましい。 The reflective color tones obtained by the present invention are often light in color, but are preferable for architectural uses because they cause little color stimulation.
又、室外側、即ちガラス面側の反射色が淡色調
のため、室内側即ち膜面側の反射色も中性色に近
い。このため夜間に室内照明などによつて不快感
を与える事が少ない。 Furthermore, since the reflected color on the outside side, that is, on the glass surface side, is light in tone, the reflected color on the indoor side, that is, on the membrane side, is also close to a neutral color. Therefore, indoor lighting at night does not cause discomfort.
又、本発明の３層構成を使用すれば、ここで示
したグリーン色、ブルー色、以外の色調も作成可
能である。さらに、このグリーン色、ブルー色、
の反射色調も、顧客の要求によつてわずかに変化
させる事ができる。 Further, by using the three-layer structure of the present invention, it is possible to create colors other than green and blue shown here. Furthermore, this green color, blue color,
The reflected color tone can also be slightly changed according to customer requirements.
本発明で使用している第１層のTiO2層は酸化
物であるため、ガラス基板のシラノール基と化学
結合をする。又、このTiO2はTiNxとも互いに相
互拡散層（TiNxOy）を形成して強く結合する。
このため、第１層のTiO2層がガラス基板と第２
層のTiNx層との付着層の役割をする。その結果
として、内部応力による膜はがれを防止する。 Since the first TiO 2 layer used in the present invention is an oxide, it chemically bonds with the silanol groups of the glass substrate. Further, this TiO 2 and TiNx form an interdiffused layer (TiNxOy) and are strongly bonded to each other.
For this reason, the first layer of TiO2 is connected to the glass substrate and the second layer.
The layer acts as an adhesion layer with the TiNx layer. As a result, film peeling due to internal stress is prevented.
一方、第３層のTiO2層は、第２層のTiNx（ｘ
＞1.0）に対して保護層の役割をする。この保護
層があるため、膜の耐久性が、向上しTiN，
TiNx（ｘ＞1.0）の製膜の際の基板加熱が不要に
なる。 On the other hand, the third TiO2 layer is the second layer TiNx (x
>1.0). Because of this protective layer, the durability of the film is improved.
No need to heat the substrate during TiNx (x>1.0) film formation.
なお、上記した３層構成の熱線反射膜の上層又
は下層に更にその他種類の各種層を積層させても
よい。 Note that various other types of layers may be further laminated on the upper or lower layer of the above-described three-layer heat ray reflective film.
［実施例］ 以下に本発明の実施例について説明する。[Example] Examples of the present invention will be described below.
実施例 １
マグネトロンD.C.スパツタ装置の陰極上に金属
Tiのターゲツトをセツトする。研磨などの方法
で６mm厚のソーダライムガラス基板を十分に洗
浄、乾燥した後、真空槽内に入れ、油拡散ポンプ
で１×10-5Torr以下まで排気する。この際基板
加熱は行なわない。次にO2ガスを真空系内へ導
入し、その圧力が3.40×10-3Torrになるように調
節する。この状態で金属チタンターゲツトへ
6.4W／cm2のパワーを印加し、３分間プレスパツ
タを行い、TiO2膜を75Å製膜する。次に真空系
内の雰囲気を100％純N2ガスに完全に置換し、そ
の圧力が3.20×10-3Torrになるように調節する。
この状態で金属チタンターゲツトへ5.3W／cm2の
パワーを印加し、同じく３分間プレスパツタを行
なつて、TiNxを285Å製膜する。最後に真空系
内の雰囲気を再び100％O2ガスに戻し、圧力が
3.40×10-3Torrになるようにする。そして同じ様
に6.4W／cm2のパワーを印加し、３分間プレスパ
ツタを行ない、TiO2膜を150Å製膜する。尚、膜
厚の制御はすべて、ターゲツトの前を通過するガ
ラス基板の搬送速度を変化させる事によつて行な
う。Example 1 Metal on the cathode of a magnetron DC sputtering device
Set the Ti target. After thoroughly cleaning and drying a 6 mm thick soda lime glass substrate by polishing or other methods, it is placed in a vacuum chamber and evacuated to below 1×10 -5 Torr using an oil diffusion pump. At this time, the substrate is not heated. Next, O 2 gas is introduced into the vacuum system and the pressure is adjusted to 3.40×10 −3 Torr. In this state, go to the metal titanium target.
A power of 6.4 W/cm 2 was applied and press sputtering was performed for 3 minutes to form a TiO 2 film with a thickness of 75 Å. Next, the atmosphere in the vacuum system is completely replaced with 100% pure N 2 gas, and the pressure is adjusted to 3.20×10 -3 Torr.
In this state, a power of 5.3 W/cm 2 was applied to the metal titanium target, and press sputtering was performed for 3 minutes to form a TiNx film of 285 Å. Finally, the atmosphere in the vacuum system is returned to 100% O 2 gas, and the pressure is
Set it to 3.40×10 -3 Torr. Then, in the same way, a power of 6.4 W/cm 2 was applied and press sputtering was performed for 3 minutes to form a TiO 2 film of 150 Å. The film thickness is controlled by changing the transport speed of the glass substrate passing in front of the target.
この様にして得られた３層膜の付き熱線反射ガ
ラスの分光反射スペクトルを測定した結果は第２
図の曲線５の通りであり、又その可視スペクトル
帯域での分光透過率は35％、膜面側の分光反射率
は27％、ガラス面側の分光反射は29％であつた。
又、その反射色調はガラス面側がｘ＝0.280，ｙ
＝0.313で淡色調のブルー色を呈し、膜面側がｘ
＝0.307，ｙ＝0.337のほとんど中性色であつた。
測定の際の標準色光としてはＤ光源（ｘ＝0.313，
ｙ＝0.329）を用いた。 The results of measuring the spectral reflection spectrum of the heat ray reflective glass with the three-layer film obtained in this way are as follows.
As shown in curve 5 in the figure, the spectral transmittance in the visible spectrum band was 35%, the spectral reflectance on the film surface side was 27%, and the spectral reflection on the glass surface side was 29%.
Also, the reflected color tone is x = 0.280, y on the glass side.
= 0.313, it exhibits a light blue color, and the film side is x
= 0.307, y = 0.337, almost neutral color.
D light source (x=0.313,
y=0.329) was used.
得られたサンプルの耐久性を調べるため、消し
ゴムで1000回擦傷試験を行なつた所、その透過率
の変化量は＋0.5％であつた。 In order to examine the durability of the obtained sample, a scratch test was performed 1000 times with an eraser, and the change in transmittance was +0.5%.
実施例 ２
実施例１と同様の手順で、６mm厚のソーダライ
ムガラス基板上に160Å厚のTiO2膜、400Å厚の
TiNx膜、120Å厚のTiO2膜を順次積層した。得
られた３層膜付き熱線反射ガラスの分光反射スペ
クトルを測定した結果は第２図の曲線６の通りで
あり、又その可視スペクトル帯域での分光透過率
は28％、膜面側の分光反射率は24％、ガラス面側
の分光反射率は22％であつた。又、その反射色調
はガラス側面がｘ＝0.323，ｙ＝0.364で淡色調の
グリーン色を呈し、膜面側はｘ＝0.350，ｙ＝
0.377でわずかに黄味を帯びていた。Example 2 Using the same procedure as in Example 1, a 160 Å thick TiO 2 film and a 400 Å thick TiO 2 film were deposited on a 6 mm thick soda lime glass substrate.
A TiNx film and a 120 Å thick TiO 2 film were sequentially laminated. The result of measuring the spectral reflection spectrum of the obtained heat-reflecting glass with three-layer film is as shown in curve 6 in Figure 2, and the spectral transmittance in the visible spectrum band is 28%, and the spectral reflection on the film side is as follows. The spectral reflectance on the glass surface side was 22%. Also, the reflected color tone is a light green color on the glass side at x=0.323, y=0.364, and on the film side, x=0.350, y=
It was 0.377 and had a slight yellowish tinge.
このサンプルに実施例１と同様に、消しゴム
1000回の擦傷試験を行つた所、その透過率の変化
量は−0.4％であつた。 Add an eraser to this sample as in Example 1.
When the scratch test was performed 1000 times, the change in transmittance was -0.4%.
比較例
他の実施例と同様の手順で排気した後、実施例
３の（Ar＋N2）の混合ガスを用いて、直接ガラ
ス基上にTiN膜を505Å製膜する。なお、第１層
及び第３層のTiO2膜も省略する。Comparative Example After evacuation in the same manner as in the other Examples, a TiN film of 505 Å was formed directly on the glass substrate using the (Ar+N 2 ) mixed gas of Example 3. Note that the TiO 2 films of the first and third layers are also omitted.
このサンプルにも、消しゴム1000回の擦傷試験
を行なつた所、その透過率の変化量は＋2.3％と
やや大きく、又擦傷跡も他のサンプルに比べて目
立ち気味であつた。 When this sample was also subjected to a scratch test using an eraser 1000 times, the change in transmittance was rather large at +2.3%, and the scratches were more noticeable than other samples.
［発明の効果］
本発明は、TiN膜単層では実現不可能なグリ
ーン色、ブルー色、などの反射色調を表現する事
ができ、又膜厚構成を変化させれば他の色調も表
現できるなど優れた効果を有する。[Effects of the Invention] The present invention can express reflection tones such as green and blue that cannot be achieved with a single layer of TiN film, and other tones can also be expressed by changing the film thickness structure. It has excellent effects such as
又、同じグリーン色の反射色調でも膜厚をわず
かに変動させる事によつて顧客の要求に応じて、
その色調を変化させる事ができるという利点があ
る。さらに第１層のTiO2層、第３層のTiO2層が
それぞれ保護膜、付着膜の役割をし、膜全体の耐
久製を向上させるという効果も認められる。 In addition, by slightly varying the film thickness even with the same reflective color tone of green, we can respond to customer requests.
It has the advantage of being able to change its color tone. Furthermore, the first layer of TiO 2 and the third layer of TiO 2 serve as a protective film and an adhesion film, respectively, and are also effective in improving the durability of the entire film.
第１図は、本発明により得られた熱線反射ガラ
スの膜構成を示すための熱線反射ガラスの断面図
であり、第２図は実施例１〜３によつて得られた
各色調系の熱線反射ガラスの可視域における反射
分光スペクトルを示す図である。
１……ガラス基板、２……第１層のTiO2層、
３……第２層のTiNx層、４……第３層のTiO2
層、５……ブルー色反射の分光反射スペクトル
（実施例１）、６……グリーン色反射の分光反射ス
ペクトル（実施例２）。
FIG. 1 is a cross-sectional view of the heat ray reflective glass to show the film structure of the heat ray reflective glass obtained according to the present invention, and FIG. FIG. 3 is a diagram showing a reflection spectrum of reflective glass in the visible range. 1...Glass substrate, 2...First layer of TiO 2 layer,
3...Second layer TiNx layer, 4...Third layer TiO 2
Layer 5... Spectral reflection spectrum of blue color reflection (Example 1), 6... Spectral reflection spectrum of green color reflection (Example 2).
Claims (1)
中で10Å〜200Åの厚さを有する酸化チタン
（TiO2）層を物理蒸着法により形成し、次いで前
記第１層上に第２層として純窒素雰囲気中で窒化
チタン（TiNx，ｘ＞1.0）層をスパツタリング法
により形成し、更にその第２層上に第３層として
酸素含有雰囲気中で10Å〜200Åの厚さを有する
酸化チタン（TiO2）層を物理蒸着法により形成
することを特徴とする可視スペクトル帯域で40％
以下の透過率及び熱線に対する高い反射能を有す
る熱線反射ガラスの製法。 ２ 物理蒸着法が陰極スパツタリング法であるこ
とを特徴とする特許請求の範囲第１項記載の熱線
反射ガラスの製法。 ３ 第２層として純窒素雰囲気中で200Å〜1000
Åの厚みを有する窒化チタン（TiNx，ｘ＞1.0）
層をスパツタリング法により形成することを特徴
とする特許請求の範囲第１項記載の熱線反射ガラ
スの製法。 ４ 第１層の酸化チタン（TiO2）層の厚みが50
Å〜100Å、第２層の窒化チタン（TiNx，ｘ＞
1.0）層の厚みが255Å〜315Å、第３層の酸化チ
タン（TiO2）層の厚みが125Å〜175Åであり、
そのガラス基板側からの反射色調がブルー色を呈
する特許請求の範囲第１項記載の熱線反射ガラス
の製法。 ５ 第１層の酸化チタン（TiO2）層の厚みが140
Å〜180Å、第２層の窒化チタン（TiNx，ｘ＞
1.0）層の厚みが、375Å〜425Å、第３層の酸化
チタン（TiO2）層の厚みが85Å〜155Åであり、
そのガラス基板側からの反射色調がグリーン色を
呈する特許請求の範囲第１項記載の熱線反射ガラ
スの製法。 ６ 第１層の酸化チタン（TiO2）層の厚みが90
Å〜130Å、第２層の窒化チタン（TiNx，ｘ＞
1.0）層の厚みが、380Å〜420Å、第３層の酸化
チタン（TiO2）層の厚みが155Å〜200Åであり、
そのガラス基板側からの反射色調がグリーン色を
呈する特許請求の範囲第１項記載の熱線反射ガラ
スの製法。[Claims] 1. A titanium oxide (TiO 2 ) layer having a thickness of 10 Å to 200 Å is formed as a first layer on a glass substrate by physical vapor deposition in an oxygen-containing atmosphere, and then on the first layer. A titanium nitride (TiNx, x>1.0) layer is formed by sputtering in a pure nitrogen atmosphere as a second layer, and a third layer with a thickness of 10 Å to 200 Å is formed on the second layer in an oxygen-containing atmosphere. 40% in the visible spectrum band, characterized by the formation of a titanium oxide (TiO 2 ) layer by physical vapor deposition.
A method for producing heat ray reflective glass having the following transmittance and high reflective ability against heat rays. 2. The method for producing heat ray reflective glass according to claim 1, wherein the physical vapor deposition method is a cathode sputtering method. 3 200 Å to 1000 Å in pure nitrogen atmosphere as the second layer
Titanium nitride (TiNx, x > 1.0) with a thickness of Å
A method for producing a heat ray reflective glass according to claim 1, characterized in that the layer is formed by a sputtering method. 4 The thickness of the first titanium oxide (TiO 2 ) layer is 50
Å~100Å, second layer titanium nitride (TiNx, x>
1.0) The thickness of the layer is 255 Å to 315 Å, and the thickness of the third titanium oxide (TiO 2 ) layer is 125 Å to 175 Å,
The method for producing a heat ray reflective glass according to claim 1, wherein the reflected color from the glass substrate side is blue. 5 The thickness of the first titanium oxide (TiO 2 ) layer is 140
Å~180Å, second layer titanium nitride (TiNx, x>
1.0) The thickness of the layer is 375 Å to 425 Å, and the thickness of the third titanium oxide (TiO 2 ) layer is 85 Å to 155 Å,
2. The method for producing a heat ray reflective glass according to claim 1, wherein the reflected color from the glass substrate side is green. 6 The thickness of the first titanium oxide (TiO 2 ) layer is 90
Å~130Å, second layer titanium nitride (TiNx, x>
1.0) The thickness of the layer is 380 Å to 420 Å, and the thickness of the third titanium oxide (TiO 2 ) layer is 155 Å to 200 Å,
2. The method for producing a heat ray reflective glass according to claim 1, wherein the reflected color from the glass substrate side is green.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1857987A JPS63190742A (en) | 1987-01-30 | 1987-01-30 | Production of heat-ray reflecting glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1857987A JPS63190742A (en) | 1987-01-30 | 1987-01-30 | Production of heat-ray reflecting glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63190742A JPS63190742A (en) | 1988-08-08 |
| JPH0460061B2 true JPH0460061B2 (en) | 1992-09-25 |
Family
ID=11975538
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1857987A Granted JPS63190742A (en) | 1987-01-30 | 1987-01-30 | Production of heat-ray reflecting glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63190742A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63252944A (en) * | 1987-04-10 | 1988-10-20 | Nippon Sheet Glass Co Ltd | Transparent heat radiation-reflecting sheet |
| JPH0243487A (en) * | 1988-04-19 | 1990-02-14 | Nippon Sheet Glass Co Ltd | Board for shielding heat ray having high visible radiation permeability |
| JPH0251693U (en) * | 1988-10-06 | 1990-04-12 | ||
| GB9414957D0 (en) * | 1994-07-25 | 1994-09-14 | Glaverbel | A pyrolytically coated glazing panel |
| US7588829B2 (en) * | 2002-05-31 | 2009-09-15 | Ppg Industries Ohio, Inc. | Article having an aesthetic coating |
| CN105026606B (en) * | 2013-05-15 | 2018-03-27 | 株式会社尼康 | The manufacture method of compound film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6036355A (en) * | 1983-03-31 | 1985-02-25 | ライボルト・アクチェンゲゼルシャフト | Manufacture of plate with permeability of 5-40 percents in visible spectrum zone and reflectivity against heat ray |
| JPS60187671A (en) * | 1984-03-06 | 1985-09-25 | Asahi Glass Co Ltd | Formation of laminated film by reactive sputtering method |
-
1987
- 1987-01-30 JP JP1857987A patent/JPS63190742A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6036355A (en) * | 1983-03-31 | 1985-02-25 | ライボルト・アクチェンゲゼルシャフト | Manufacture of plate with permeability of 5-40 percents in visible spectrum zone and reflectivity against heat ray |
| JPS60187671A (en) * | 1984-03-06 | 1985-09-25 | Asahi Glass Co Ltd | Formation of laminated film by reactive sputtering method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63190742A (en) | 1988-08-08 |
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