JPH03112833A - Heat-ray shielding glass - Google Patents
Heat-ray shielding glassInfo
- Publication number
- JPH03112833A JPH03112833A JP25129589A JP25129589A JPH03112833A JP H03112833 A JPH03112833 A JP H03112833A JP 25129589 A JP25129589 A JP 25129589A JP 25129589 A JP25129589 A JP 25129589A JP H03112833 A JPH03112833 A JP H03112833A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- thickness
- ray shielding
- heat ray
- glass plate
- 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.)
- Pending
Links
- 239000011521 glass Substances 0.000 title claims abstract description 101
- 239000010410 layer Substances 0.000 claims abstract description 107
- 239000011248 coating agent Substances 0.000 claims abstract description 31
- 238000000576 coating method Methods 0.000 claims abstract description 31
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 29
- 238000004544 sputter deposition Methods 0.000 claims abstract description 19
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 9
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- 239000011241 protective layer Substances 0.000 claims description 38
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 claims description 18
- 239000005329 float glass Substances 0.000 claims description 11
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 abstract description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 abstract description 23
- 239000001301 oxygen Substances 0.000 abstract description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 16
- 238000005299 abrasion Methods 0.000 abstract description 14
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract description 12
- 239000011247 coating layer Substances 0.000 abstract 1
- 239000005357 flat glass Substances 0.000 description 16
- 239000010936 titanium Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 12
- 229910052719 titanium Inorganic materials 0.000 description 12
- 235000019646 color tone Nutrition 0.000 description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 229910000906 Bronze Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 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
- 150000004767 nitrides Chemical class 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 101100481408 Danio rerio tie2 gene Proteins 0.000 description 1
- 101100481410 Mus musculus Tek gene Proteins 0.000 description 1
- -1 O□ film or SnO2 film Chemical class 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910007948 ZrB2 Inorganic materials 0.000 description 1
- SQWOCMZNVYUDSE-UHFFFAOYSA-N [Zr+4].[Zr+4].[Zr+4].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] SQWOCMZNVYUDSE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- VWZIXVXBCBBRGP-UHFFFAOYSA-N boron;zirconium Chemical compound B#[Zr]#B VWZIXVXBCBBRGP-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000004313 glare Effects 0.000 description 1
- 229940110676 inzo Drugs 0.000 description 1
- 239000005340 laminated glass Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 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、透明なガラス板上に、耐摩耗強度が大きい保
護層を最上層にもつガラス板に関し、とりわけ自動車や
建築用の窓ガラスに通した熱線遮へい性を有するガラス
に関するものである。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a glass plate having a protective layer with high abrasion resistance as the uppermost layer on a transparent glass plate, and is particularly applicable to window glass for automobiles and buildings. This relates to glass that has heat ray shielding properties that allow it to pass through.
可視光線の一部を透過させ、太陽光エネルギーの一部を
遮へいする性能をもった熱線遮へいガラスを、車輌や建
築物の窓ガラスに用いることにより室内の冷房負荷を減
することができる。この目的に適したガラスとしては、
特開昭63−206332で開示されているガラス板/
TiOア膜/ZrN膜/TiO2膜の構成の熱線遮へい
ガラスや、特開昭64−5930で開示されているガラ
ス板/SnO□膜/TiO2膜/TiN膜/TiO□膜
/SnO□膜の構成の熱!遮へいガラスがある。また特
開昭63−206333で開示されているたとえば、ガ
ラス板/Ti01膜/ZrN膜/Ti01膜/SiO!
膜の構成の熱線遮へいガラスは、建築物や自動車の窓ガ
ラスとして合せガラスにすることなく、単板タイプで使
用し得ることが示されている。Heat ray shielding glass, which has the ability to transmit a portion of visible light and block a portion of solar energy, can be used in the window glass of vehicles and buildings to reduce the indoor cooling load. Glass suitable for this purpose is
Glass plate disclosed in JP-A No. 63-206332/
Heat ray shielding glass with a TiO film/ZrN film/TiO2 film structure, and a glass plate/SnO□ film/TiO2 film/TiN film/TiO□ film/SnO□ film structure disclosed in JP-A-64-5930. The fever! There is a shielding glass. Further, for example, glass plate/Ti01 film/ZrN film/Ti01 film/SiO! disclosed in JP-A No. 63-206333!
It has been shown that heat ray shielding glass with a membrane structure can be used as a single-pane type as window glass for buildings and automobiles, without having to be laminated.
これらの従来技術による熱線遮へいガラスは、いずれも
空気に触れる最上層は、TiO2、 SnO2、 Si
O□などの耐久性が強いとされている酸化物の膜が用い
られている。In all of these conventional heat shielding glasses, the top layer exposed to air is made of TiO2, SnO2, or Si.
An oxide film such as O□, which is said to be highly durable, is used.
建築物や車輌用の窓ガラスの如き、ガラス板上に設けら
れた被覆が直接大気に触れる状態で用いられる場合、被
覆は実用上耐え得る機械的強度および化学的耐久性を必
要とするが、とりわけスクラッチに対する耐摩耗性が要
求される。そして、被覆が、2つ以上の物質の積層体で
ある場合、被覆の耐摩耗性は最上層の物質の耐摩耗強度
により大きく左右されるので、最上層の膜の強度を向上
させることが最も重要な課題となる。When a coating provided on a glass plate is used in direct contact with the atmosphere, such as window glass for buildings or vehicles, the coating must have mechanical strength and chemical durability that can withstand practical use. In particular, wear resistance against scratches is required. When the coating is a laminate of two or more materials, the abrasion resistance of the coating is largely determined by the abrasion resistance strength of the top layer material, so it is best to improve the strength of the top layer film. This will be an important issue.
しかしながら従来技術においては、被覆の最上層はTi
O□膜やSnO2膜の如き比較的摩耗性の強い金属酸化
物を用いたり、5i02膜を厚く被覆したものであり、
実用上必ずしも満足な耐久性をそなえていない。そして
とくに自動車用の側面または後部の窓ガラスに熱線遮へ
いガラスを用いる場合、さらに耐摩耗性のある膜が被覆
された熱線遮へいガラスが望まれていた。However, in the prior art, the top layer of the coating is Ti
It uses relatively abrasive metal oxides such as O□ film or SnO2 film, or is coated with a thick 5i02 film.
It does not necessarily have sufficient durability for practical use. Particularly when heat ray shielding glass is used for the side or rear window glass of an automobile, a heat ray shielding glass coated with a more wear-resistant film has been desired.
本発明は、上記した従来技術が有する問題点を改善し、
耐摩耗性が改善された熱線遮へいガラスを提供するにあ
る。The present invention improves the problems of the above-mentioned prior art,
An object of the present invention is to provide heat ray shielding glass with improved abrasion resistance.
本発明は、透明なガラス板、前記透明なガラス板上に被
覆された熱線遮へい性の被膜、前記被膜の上に被覆され
た保護層からなる熱線遮へいガラスである。前記保護層
は、硼化ジルコニウムからなるターゲットを減圧された
酸化性ガスを含む雰囲気中でスパッタリングすることに
より被覆された、硼化ジルコニウムと酸化性ガスとの反
応生成物が好ましい。The present invention is a heat ray shielding glass comprising a transparent glass plate, a heat ray shielding coating coated on the transparent glass plate, and a protective layer coated on the coating. The protective layer is preferably a reaction product of zirconium boride and an oxidizing gas, which is coated by sputtering a target made of zirconium boride in a reduced pressure atmosphere containing an oxidizing gas.
本発明の熱線遮へいガラスの保護層は、ZrB、Oyか
らなる化学式で表わされる。用いる硼化ジルコニウムタ
ーゲットの組成は、通常ZrBtなる組成のものが用い
られる。また酸化性雰囲気は、炭酸ガス、−酸化炭素、
酸素を用いることができるが、酸素が最も好ましく用い
られる。本発明にかかる保護層の酸素含有率は、硼化ジ
ルコニウムターゲットをスパツクするときの雰囲気中の
酸化性ガスの分圧を調整することによりおこなわれる。The protective layer of the heat ray shielding glass of the present invention is represented by a chemical formula consisting of ZrB and Oy. The composition of the zirconium boride target used is usually ZrBt. In addition, the oxidizing atmosphere includes carbon dioxide gas, -carbon oxide,
Although oxygen can be used, oxygen is most preferably used. The oxygen content of the protective layer according to the present invention is determined by adjusting the partial pressure of the oxidizing gas in the atmosphere when sprocketing the zirconium boride target.
反応生成物の酸素量は膜の吸収が実質上生じないように
調整され、好ましくは屈折率が1.7〜2.0になるよ
うに調整される。保護膜を被覆するときの減圧された雰
囲気ガス中の酸素の量は硼化ジルコニウムの被覆スピー
ドに関係し、一義的に定めることは困難であるが、通常
20〜90%の酸素を含むガスが用いられる。また保護
層が実用上必要な摩耗強度を具備するには、膜の厚みは
5rv以上であることが好ましい。The amount of oxygen in the reaction product is adjusted so that substantially no absorption occurs in the film, and preferably so that the refractive index is 1.7 to 2.0. The amount of oxygen in the reduced pressure atmosphere gas when coating the protective film is related to the coating speed of zirconium boride, and is difficult to determine unambiguously, but usually a gas containing 20 to 90% oxygen is used. used. Further, in order for the protective layer to have practically necessary abrasion strength, the thickness of the film is preferably 5 rv or more.
本発明にかかる透明なガラス板上に設けられる被膜は、
とくに限定されるものではなく、単層からなる膜であっ
ても2層以上の積層体からなる膜であってもよい。たと
えば、それ自身で近赤外域の波長に対して反射性を有す
る窒化チタニウム。The coating provided on the transparent glass plate according to the present invention is
There are no particular limitations, and the film may be a single layer or a laminate of two or more layers. For example, titanium nitride, which itself is reflective to near-infrared wavelengths.
窒化ジルコニウムなどの窒化物の膜や、これら窒化物の
膜とTie、膜、 Sn0w膜、 Zr0z膜、 Ta
205膜。Nitride films such as zirconium nitride, films of these nitrides and Tie films, Sn0w films, Zr0z films, Ta
205 membrane.
InzO,膜、 ZnO膜、 ITO膜などの可視域で
透明な膜とを積層したものを用いることができる。また
、可視域で透明な高屈折率の膜と低屈折率の膜を交互に
積層した波長選択性を有する積層体を用いることができ
る。A stack of films transparent in the visible range, such as InzO, ZnO, ITO, etc., can be used. Furthermore, a laminate having wavelength selectivity in which transparent films with a high refractive index and films with a low refractive index that are transparent in the visible region are alternately laminated can be used.
本発明は、透明なガラス板の上に被覆された熱線遮へい
性の被膜が、ガラス板側から数えて第1層として50〜
7Onmの厚みの5nOz、第2層として40〜65n
mの厚みのTiO2からなり、前記保護層の厚みが35
〜7Onmであるものが用いられる。In the present invention, a heat ray shielding film coated on a transparent glass plate serves as a first layer of 50 to
5nOz with 7Onm thickness, 40-65n as second layer
The protective layer is made of TiO2 with a thickness of 35 m.
~7 Onm is used.
かかる熱線遮へいガラスは、可視光線透過率が70%以
上で窓ガラスどして明るく、かつ、太陽光エネルギーを
遮へいする性能を有しているとともに、単板で使用し得
る耐摩耗強度を有している。Such heat ray shielding glass has a visible light transmittance of 70% or more, is brighter than window glass, has the ability to shield sunlight energy, and has abrasion resistance that can be used as a single sheet. ing.
また熱aXへいガラスの反射色調および透過色調を、用
いるガラス板から大きく変えないというとくに自動車の
忘ガラスに好適なガラスとするためには、第1層のSn
O,の厚みが55〜650111、第2層のTi01の
厚みが45〜6Onm、保護層の厚みが50〜65nm
であることが好ましい。In addition, in order to make the reflection and transmission color tones of the thermal aX glass not significantly different from the glass plate used, which is particularly suitable for automotive glass, it is necessary to
The thickness of O, is 55-650111 nm, the thickness of the second layer Ti01 is 45-6 Onm, and the thickness of the protective layer is 50-65 nm.
It is preferable that
上記した透明なガラス板の上に被覆された熱線遮へい性
の被膜は、太陽光エネルギーの遮へい性能を向上させ、
あるいは色調を微妙に調整するために、さらに10rv
を越えない厚みの窒化チタニウム層または4On−を越
えない厚みのSnO□層の少なくとも1つを、前記窒化
チタニウム層については第1層と第2層との間に、前記
SnO□層については第2層と保護層との間に設けるこ
とができる。The heat ray shielding film coated on the transparent glass plate described above improves the solar energy shielding performance,
Or to finely adjust the color tone, add an additional 10rv.
at least one of a titanium nitride layer with a thickness not exceeding 4 On- or a SnO It can be provided between the two layers and the protective layer.
また本発明は、前記透明なガラス板の上に被覆された熱
線遮へい性の被膜が、2〜10nn+の厚みの窒化ジル
コニウム層であって、前記保護層の厚みを5〜80nm
とすることができる。かかる熱線遮へいガラスは、可視
光線透過率が70%以上で窓ガラスとして明るく、かつ
、太陽光エネルギーを遮へいする性能を有しているとと
もに、単板で使用し得る耐摩耗強度を有している。また
熱線遮へいガラスの反射色調および透過色調を、用いる
透明のガラス板から大きく変えないという自動車の窓ガ
ラスに好適なガラスとするためには、前記窒化ジルコニ
ウム層の厚みが3〜8nm、保護層の厚みが7〜70n
mの範囲であることが好ましい。Further, in the present invention, the heat ray shielding film coated on the transparent glass plate is a zirconium nitride layer with a thickness of 2 to 10 nm+, and the thickness of the protective layer is 5 to 80 nm.
It can be done. Such heat ray shielding glass has a visible light transmittance of 70% or more, is bright as window glass, has the ability to shield sunlight energy, and has abrasion resistance strength that allows it to be used as a veneer. . In addition, in order to make the heat ray shielding glass suitable for automobile window glass without significantly changing the reflected color tone and transmitted color tone from the transparent glass plate used, the thickness of the zirconium nitride layer should be 3 to 8 nm, and the thickness of the protective layer should be 3 to 8 nm. Thickness is 7~70n
The range is preferably m.
また上記した熱線遮へいガラスは、とりわけ反射色調を
微妙に調整するために、さらに6Onmを越えない厚み
のTiO□層を透明なガラス板と前記窒化ジルコニウム
層との間に設けるか、3Onmを越えない厚みのTiO
□層を前記窒化ジルコニウム層と前記保護層との間に設
けるか、あるいは同時に窒化ジルコニウム層をはさむよ
うにして設けることができる。In addition, in order to finely adjust the reflected color tone, the heat ray shielding glass described above is further provided with a TiO□ layer with a thickness not exceeding 6 Onm between the transparent glass plate and the zirconium nitride layer, or with a thickness not exceeding 3 Onm. Thickness of TiO
The □ layer may be provided between the zirconium nitride layer and the protective layer, or may be provided simultaneously with the zirconium nitride layer sandwiched therebetween.
また、本発明は、前記透明なガラス板の上に被覆された
熱線遮へい性の被膜が、ガラス板側から数えて第1層と
して20〜60nmの厚みのSnO□。Further, in the present invention, the heat ray shielding film coated on the transparent glass plate has a thickness of 20 to 60 nm as a first layer counted from the glass plate side.
第2層として2〜2Onamの厚みのTi01.第3層
として2〜20nmの厚みの窒化チタニウム、第4層と
して2〜20nmの厚みのTiO□が被覆された積層膜
で、前記保護層の厚みが10〜80nmとすることがで
きる。かかる熱線遮へいガラスは、可視光線透過率が7
0%以上で窓ガラスとして明るく、かつ、太陽光エネル
ギーを遮へいする性能を有しているとともに、単板で使
用し得る耐摩耗強度を有している。また熱線遮へいガラ
スの反射色調、透過色調を用いる透明のガラス板から大
きく変えないという自動車の窓ガラスに好適なガラスと
するためには、前記第1層のSnO□の厚みが35〜4
5nm、第2層のTie、の厚みが3〜10no+、第
3層の窒化チタニウムの厚みが3〜10nra、第4層
のTi0zが3〜10nm、保護膜の厚みが50〜65
nmであることが好ましい。上記した熱線遮へいガラス
の、とりわけ反射色調を微妙に調整するために、さらに
第4層と保護層との間に、60nmの厚みを越えないS
nO□層を設けることができる。The second layer is Ti01 with a thickness of 2 to 2 Onam. The laminated film is coated with titanium nitride with a thickness of 2 to 20 nm as the third layer, and TiO□ with a thickness of 2 to 20 nm as the fourth layer, and the thickness of the protective layer can be 10 to 80 nm. Such heat ray shielding glass has a visible light transmittance of 7.
At 0% or more, it is bright as a window glass, has the ability to shield sunlight energy, and has abrasion resistance that can be used as a veneer. In addition, in order to make a glass suitable for automobile window glass that does not significantly change the reflection color tone and transmission color tone of the heat ray shielding glass from transparent glass plates, the thickness of the first layer of SnO□ must be 35 to 4.
5nm, the thickness of the second layer Tie is 3 to 10no+, the thickness of the third layer titanium nitride is 3 to 10nra, the fourth layer TiOz is 3 to 10nm, and the thickness of the protective film is 50 to 65.
It is preferably nm. In order to finely adjust the reflective color tone of the above-mentioned heat ray shielding glass, a layer of Sulfur with a thickness not exceeding 60 nm is added between the fourth layer and the protective layer.
An nO□ layer can be provided.
また、本発明は前記透明なガラス板の上に被覆された被
膜が、ガラス板側から数えて第1層として80〜130
nl11の厚みのTiO2,第2層として160〜23
01111の厚みのSiO2,第3層として80〜13
0nmの厚みのT iOz *第4層として30〜80
n−の厚みの5iO1が被覆された積層膜で、前記保護
層の厚みを40〜80nmとすることができる。かかる
熱線遮へいガラスは、可視光線透過率が70%以上で窓
ガラスとして明るく、かつ、太陽光エネルギーを遮へい
する性能を有しているととに、単板で使用し得る耐摩耗
強度を有している。Further, the present invention provides that the film coated on the transparent glass plate has a coating film of 80 to 130 as the first layer counted from the glass plate side.
TiO2 with a thickness of nl11, 160-23 as the second layer
SiO2 with a thickness of 01111, 80-13 as the third layer
0nm thick TiOz *30-80 as 4th layer
In the laminated film coated with 5iO1 having a thickness of n-, the thickness of the protective layer can be 40 to 80 nm. Such heat ray shielding glass has a visible light transmittance of 70% or more, is bright as a window glass, has the ability to shield sunlight energy, and has abrasion resistance strength that can be used as a veneer. ing.
また熱線遮へいガラスの反射色調、透過色調を、用いる
透明のガラス板から大きく変えないという自動車の窓ガ
ラスに好適なガラスとするためには、前記第1層(7)
T i Otの厚みが90〜110nm、第2層(7
)SiO,(7)厚ミM90〜110nm、第3層(7
)T i 02の厚みが18〜22nm、第4層の5i
(h(7)厚みが50〜65nllで、保護層の厚みが
60〜75nmであることが好ましい。In addition, in order to make the heat ray shielding glass suitable for automobile window glass without significantly changing the reflection color tone and transmission color tone from the transparent glass plate used, the first layer (7)
The thickness of T i Ot is 90 to 110 nm, the second layer (7
) SiO, (7) thickness M90-110 nm, third layer (7
) T i 02 thickness is 18-22 nm, fourth layer 5i
(h(7) It is preferable that the thickness is 50 to 65 nm, and the thickness of the protective layer is 60 to 75 nm.
本発明にかかる熱線遮へいガラスの透明なガラス板と保
護層との間に設けられる、金属酸化物の膜や金属窒化物
の膜は、通常用いられる金属をターゲットとして、減圧
された酸素あるいは窒素を反応ガスとする反応スパッタ
リング法や反応性アーク蒸着法により被覆することがで
きる。The metal oxide film or metal nitride film provided between the transparent glass plate and the protective layer of the heat ray shielding glass according to the present invention targets commonly used metals and irradiates them with reduced pressure oxygen or nitrogen. The coating can be performed by a reactive sputtering method or a reactive arc evaporation method using a reactive gas.
また本発明にかかる熱線遮へいガラスにかかる透明なガ
ラス板としては、透明フロートガラスやブロンズ、グレ
ー、ブルーなどの着色フロートガラスを用いることがで
きる。Further, as the transparent glass plate for the heat ray shielding glass according to the present invention, transparent float glass or colored float glass such as bronze, gray, or blue can be used.
本発明の熱線遮へいガラスの空気に接する最上層として
被覆される硼化ジルコニウムの酸化物からなる保護層は
、透明なガラス板の上に被覆された熱線遮へい性の被膜
を、摩耗、スクラッチなどの機械的外力から保護し、キ
ズを生じにくくする。The protective layer made of zirconium boride oxide, which is coated as the uppermost layer in contact with the air of the heat ray shielding glass of the present invention, protects the heat ray shielding film coated on the transparent glass plate from wear, scratches, etc. Protects from external mechanical forces and prevents scratches.
さらに、前記硼化ジルコニウムの酸化物からなる保護層
は、その厚みおよび屈折率が調整されることにより、熱
線遮へいガラスの可視光反射率を低くする。Furthermore, the thickness and refractive index of the protective layer made of the zirconium boride oxide are adjusted to lower the visible light reflectance of the heat shielding glass.
実施例
第1図は本発明にかかるガラス板の一部断面図で、1は
透明なガラス板、2は透明なガラス板l上に被覆された
熱線遮へい性の被膜、3は硼化ジルコニウムの酸化物か
らなる保護層である。以下実施例に基いて本発明を詳述
する。Embodiment FIG. 1 is a partial sectional view of a glass plate according to the present invention, in which 1 is a transparent glass plate, 2 is a heat ray-shielding coating coated on the transparent glass plate 1, and 3 is a zirconium boride film. It is a protective layer made of oxide. The present invention will be described in detail below based on Examples.
実施例1
3つのカソードをそなえたマグネトロンスパッタ装置内
にターゲットとして、錫、チタニウム。Example 1 Tin and titanium were used as targets in a magnetron sputtering device equipped with three cathodes.
硼化ジルコニウム(ZrB、で表わされる組成)をそれ
ぞれのカソードにセントした。表面を洗浄にした4日厚
のフロートガラス板を真空槽内の基板ホルダーにセット
し、真空ポンプで1.3 X 10−”Paまで排気し
た。アルボッ50体積%、酸素50体積%の混合ガスを
真空槽内に入れ、圧力を0.4 Paにした。錫ターゲ
ットに3 W / am ”の電力を印加して、所定時
間スパッタをおこない、ガラス上に65nmの厚みのS
nO□を被覆し放電を停止した。つぎに真空槽内の雰囲
気をほぼアルボッ85体積%、窒素15体積%の混合ガ
スに置換し、0.4Paの圧カニでチタニウムターゲッ
トに5 W / cm ”の電力を印加し、所定時間ス
パッタをおこない、SnO□の上に窒化ジルコニウムの
層を5nm被覆し放電を停止した。つぎに、再び真空槽
内の雰囲気をアルボッ50体積%、酸素50体積%の混
合ガスに置換し、0.4 Paの圧力下でチタニウムタ
ーゲットに3W / cll”の電力を印加して、所定
時間スパッタをおこない45rvのTiO□を窒化ジル
コニウムの層の上に被覆し、放電を停止した。引きつづ
き雰囲気ガスをそのままにして、0.4Paの圧力下で
錫ターゲットに3W/cn”の電力を印加して、所定時
間スパッタをおこない、30n−の厚みのSnO□を窒
化ジルコニウム層の上に被覆し、放電を停止した。Zirconium boride (ZrB, composition) was placed at each cathode. A 4-day thick float glass plate with a cleaned surface was set on a substrate holder in a vacuum chamber, and the vacuum pump was used to evacuate to 1.3 x 10-”Pa.A mixed gas of 50% by volume of Albod and 50% by volume of oxygen was used. was placed in a vacuum chamber and the pressure was set to 0.4 Pa.A power of 3 W/am'' was applied to the tin target and sputtering was performed for a predetermined time to form a 65 nm thick S film on glass.
The discharge was stopped by coating nO□. Next, the atmosphere in the vacuum chamber was replaced with a mixed gas of approximately 85% by volume of Albod and 15% by volume of nitrogen, and a power of 5 W/cm was applied to the titanium target using a pressure crab of 0.4 Pa to perform sputtering for a predetermined period of time. Then, a 5 nm layer of zirconium nitride was coated on SnO□ and the discharge was stopped.Next, the atmosphere in the vacuum chamber was replaced again with a mixed gas of 50% by volume of Albod and 50% by volume of oxygen, and the atmosphere was heated to 0.4 Pa. A power of 3 W/cll'' was applied to the titanium target under a pressure of 100 mL, sputtering was performed for a predetermined time, 45 rv of TiO□ was coated on the zirconium nitride layer, and the discharge was stopped. Subsequently, while leaving the atmospheric gas as it is, a power of 3 W/cn'' was applied to the tin target under a pressure of 0.4 Pa, and sputtering was performed for a predetermined time to deposit SnO□ with a thickness of 30 n- on the zirconium nitride layer. The discharge was stopped.
最後にアルボッ30体積%、酸素70体積%の混合ガス
にほぼ完全に真空槽内を置換し、0.4 Paの圧力下
で窒化ジルコニウムターゲットに6 W / cta
”の電力を印加し、所定時間スパッタをおこない、40
nmの厚みの透明なZrB、0.なる組成の膜を被覆し
、放電およびガスの導入を停止し、ガラス板上に5層か
らなる膜が被覆された熱線反射性能を有するサンプル1
を得た。サンプル1と同様の方法により層の数、層の厚
み、ガラス板の種類を変えて、サンプル2〜7を得た。Finally, the inside of the vacuum chamber was almost completely replaced with a mixed gas of 30% by volume of Albot and 70% by volume of oxygen, and 6 W/cta was applied to the zirconium nitride target under a pressure of 0.4 Pa.
” and sputtering for a predetermined period of time.
Transparent ZrB with a thickness of 0.0 nm. Sample 1 with heat ray reflection performance, in which the glass plate is coated with a film consisting of 5 layers, and the discharge and gas introduction are stopped.
I got it. Samples 2 to 7 were obtained in the same manner as Sample 1 by changing the number of layers, the thickness of the layers, and the type of glass plate.
得られたサンプル1〜7の膜構成を第1表に光学性能、
酸およびアルカリに対する耐久性および耐摩耗性能を調
べた結果を第2表に示す。Table 1 shows the film configurations of Samples 1 to 7 obtained in terms of optical performance and
Table 2 shows the results of examining durability and wear resistance against acids and alkalis.
実施例2
実施例1と同じ装置に、ターゲットとしてチタニウム、
ジルコニウム、硼化ジルコニウム(ZrBzで示される
組成)をそれぞれのカソードにセントした。表面を洗浄
にした4層厚のフロートガラス板を真空槽内のホルダー
にいれ、真空ポンプで1、3 X 10−”Paまで排
気した。アルボッ50体積%、酸素50体積%の混合ガ
スを真空槽内に入れ、圧力を0.4 Paにした。チタ
ニウムターゲットに3W / ctrr ”の電力を印
加し、所定時間スパッタをおこない、ガラス上に60n
mの厚みのTiO2を被覆し放電を停止した。その後、
真空槽内の雰囲気をアルボッ80体積%、窒素20体積
%にほぼ完全に置換し、圧力を0.4 Paにしてジル
コニウムターゲットに5W/am”の電力を印加し所定
の時間スパッタをおこない、50nmの厚みの第1層の
TiO□を被覆し放電を停止した。その後雰囲気をアル
ゴンガス85体積%、窒素ガス15体積%にほぼ完全に
置換し、0.4Paの圧力に調整した。ジルコニウムタ
ーゲットに5 W / cm ”の電力を印加し、所定
時間スパッタをおこない、4nn+の窒化ジルコニウム
を被覆し放電を停止した9次に第1層のTi0zのとき
と同様にして第3層として15nmの厚みのTiO□を
被覆し放電を停止した。最後にアルボッ20体積%、酸
素80体積%の混合ガスに真空槽内の雰囲気をほぼ完全
に置換し、0.4 Paの圧力で硼化ジルコニウムター
ゲットに6W/cI112の電力を印加し、所定時間ス
パッタをおこない、45nmの厚みの透明なZrBxO
yなる組成の膜を被覆し放電およびガスを停止して、ガ
ラス上に4層からなる膜が被覆された熱線反射性能を有
するサンプル8を得た。同様の方法により、層の数、層
の厚み、ガラス板の種類を変えてサンプル9〜12を得
た。Example 2 The same equipment as in Example 1 was used with titanium as a target,
Zirconium and zirconium boride (composition indicated by ZrBz) were placed in each cathode. A 4-layer thick float glass plate with a cleaned surface was placed in a holder in a vacuum chamber and evacuated to 1.3 x 10-''Pa with a vacuum pump.A mixed gas of 50 vol. The titanium target was placed in a tank and the pressure was set to 0.4 Pa. A power of 3 W/ctrr was applied to the titanium target, sputtering was performed for a predetermined time, and 60 nm was deposited on the glass.
After coating TiO2 with a thickness of m, the discharge was stopped. after that,
The atmosphere in the vacuum chamber was almost completely replaced with 80% by volume of Albod and 20% by volume of nitrogen, the pressure was set to 0.4 Pa, a power of 5 W/am was applied to the zirconium target, and sputtering was performed for a predetermined period of time. The discharge was stopped by coating the first layer of TiO□ with a thickness of A power of 5 W/cm'' was applied, sputtering was carried out for a predetermined time, and the discharge was stopped after coating with 4 nn+ zirconium nitride.Next, a 15 nm thick layer was formed as the third layer in the same manner as the first layer of Ti0z. It was covered with TiO□ and the discharge was stopped. Finally, the atmosphere in the vacuum chamber was almost completely replaced with a mixed gas of 20% by volume Albod and 80% by volume oxygen, and a power of 6W/cI112 was applied to the zirconium boride target at a pressure of 0.4 Pa for a predetermined period of time. Transparent ZrBxO with a thickness of 45 nm was sputtered.
A film having a composition of y was coated, and the discharge and gas were stopped to obtain a sample 8 having a heat ray reflective property in which a film consisting of four layers was coated on glass. Samples 9 to 12 were obtained in the same manner by changing the number of layers, the thickness of the layers, and the type of glass plate.
得られたサンプル8〜12の膜構成を第3表に、光学特
性、酸およびアルカリに対する耐久性、耐摩耗性能を調
べた結果を第4表に示す。Table 3 shows the film configurations of Samples 8 to 12 obtained, and Table 4 shows the results of examining optical properties, durability against acids and alkalis, and abrasion resistance.
実施例3
実施例1と同じ装置に、ターゲットとしてチタニウム、
錫、硼化ジルコニウム(ZrBzで示される組成)をそ
れぞれのカソードにセットした。表面を洗浄にした4m
m厚のフロートガラス板を真空槽内のホルダーにいれ、
真空ポンプで1.3X10−’Paまで排気した。アル
ボッ50体積%、酸素50体積%の混合ガスを真空槽内
に入れ、圧力を0.4Paにした。錫ターゲットに3W
/c+a”の電力を印加して、所定時間スパッタをおこ
ない、ガラス上に40rv+の厚みのSnO2を被覆し
放電を停止した。Example 3 Titanium was used as a target in the same apparatus as in Example 1.
Tin and zirconium boride (composition indicated by ZrBz) were set at each cathode. 4m with cleaned surface
Place a m-thick float glass plate into a holder in a vacuum chamber.
It was evacuated to 1.3×10 −'Pa with a vacuum pump. A mixed gas of 50% by volume of Albod and 50% by volume of oxygen was placed in a vacuum chamber, and the pressure was set to 0.4 Pa. 3W on tin target
Sputtering was performed for a predetermined time by applying a power of /c+a'' to coat the glass with SnO2 with a thickness of 40 rv+, and the discharge was stopped.
真空槽内の雰囲気をアルボッ40体積%、酸素60体積
%にほぼ完全に置換し、圧力を0.4Paにしてチタニ
ウムターゲットに5 W / am ”の電力を印加し
所定の時間スパッタをおこない、10nmの厚みのTi
O2を被覆し放電を停止した。その後雰囲気をアルボッ
85体積%、窒素15体積%にほぼ完全に置換し、0.
4Paの圧力に調整した。再びチタニウムターゲットに
5 W / cm ”の電力を印加し、所定時間スパッ
タをおこない、6層mの窒化チタニウムを被覆し放電を
停止した。次に第2層のTiO2のときと同様にして第
4層として10nmの厚みのTiO□を被覆し放電を停
止した。さらにアルボッ50体積%、酸素50体積%の
混合ガスに真空槽内の雰囲気をほぼ完全に置換し、0.
4Paの圧力で錫ターゲットに3W/cIl″の電力を
印加し、所定時間スパッタをおこない、15nraの厚
みの5n02を被覆し、放電を停止した。最後にアルボ
ッ40体積%、酸素60体積%の混合ガスに真空槽内の
雰囲気をほぼ完全に置換し、0.4Paの圧力で硼化ジ
ルコニウムターゲットに6 ’w / C11”の電力
を印加し、25nmの厚みの透明なZrB、O,なる組
成の膜を被覆し、放電およびガス導入を停止してガラス
上に6層が被覆された熱線遮へい性能を有するサンプル
13を得た。同様の方法により、層の数、層の厚み、ガ
ラス板の種類を変えてサンプル14〜17を得た。得ら
れたサンプル13〜17の膜構成を第5表に光学特性、
酸およびアルカリに対する耐久性、耐摩耗性能を調べた
結果を第6表に示す。The atmosphere in the vacuum chamber was almost completely replaced with 40% by volume of Albot and 60% by volume of oxygen, the pressure was set to 0.4 Pa, a power of 5 W/am was applied to the titanium target, and sputtering was performed for a predetermined period of time to form a 10 nm film. Ti thickness of
The discharge was stopped by covering with O2. Thereafter, the atmosphere was almost completely replaced with 85% by volume of Albod and 15% by volume of nitrogen.
The pressure was adjusted to 4 Pa. A power of 5 W/cm'' was again applied to the titanium target, sputtering was performed for a predetermined time, and the discharge was stopped after covering 6 m layers of titanium nitride.Next, in the same way as the second layer of TiO2, the fourth The discharge was stopped by coating TiO□ with a thickness of 10 nm as a layer.Furthermore, the atmosphere in the vacuum chamber was almost completely replaced with a mixed gas of 50% by volume of Albod and 50% by volume of oxygen.
A power of 3 W/cIl'' was applied to the tin target at a pressure of 4 Pa, sputtering was performed for a predetermined time, 5N02 was coated with a thickness of 15 NRA, and the discharge was stopped.Finally, a mixture of 40 volume % Albot and 60 volume % oxygen The atmosphere in the vacuum chamber was almost completely replaced with gas, and a power of 6'w/C11' was applied to the zirconium boride target at a pressure of 0.4 Pa, and a transparent ZrB, O, composition with a thickness of 25 nm was prepared. After coating the film, discharging and gas introduction were stopped to obtain a sample 13 having heat ray shielding performance in which six layers were coated on glass. Samples 14 to 17 were obtained in the same manner by changing the number of layers, the thickness of the layers, and the type of glass plate. Table 5 shows the film configurations of Samples 13 to 17 obtained, and their optical properties.
Table 6 shows the results of examining durability against acids and alkalis and wear resistance.
実施例4
実施例1と同じ装置に、ターゲットとしてチタニウム、
シリコン、窒化ジルコニウム(ZrB2で示される組成
)をそれぞれのカソードにセットした。Example 4 Titanium was used as a target in the same apparatus as in Example 1.
Silicon and zirconium nitride (composition indicated by ZrB2) were set at each cathode.
表面を洗浄にした4N厚のフロートガラス板を真空槽内
のホルダーにいれ、真空ポンプで1.3×1O−3Pa
まで排気した。アルボッ50体積%、酸素50体積%の
混合ガスを真空槽内に入れ、圧力を0.4Paにした。A 4N thick float glass plate with a cleaned surface was placed in a holder in a vacuum chamber, and heated to 1.3×1O-3Pa using a vacuum pump.
Exhausted until. A mixed gas of 50% by volume of Albod and 50% by volume of oxygen was placed in a vacuum chamber, and the pressure was set to 0.4 Pa.
チタニウムターゲットに3W/(J”の電力を印加して
、所定時間スパッタをおこない、ガラス上に1100n
の厚みの第1層としてTiO□を被覆し放電を停止した
。真空槽内の雰囲気をアルボッ40体積%、酸素60体
積%にほぼ完全に置換し、圧力を0.4Paにしてシリ
コンターゲットに5W/σ2の電力を印加し所定の時間
スパッタをおこない、200nmの厚みの第2層として
SiO□を被覆し放電を停止した。その後雲囲気をアル
ボッ50体積%、酸素50体積%にほぼ完全に置換し、
0.4Paの圧力に調整した。チタニウムターゲットに
5 W / cm ”の電力を印加し、所定時間スパッ
タをおこない、1100nの第3層としてTiO□を被
覆し放電を停止した。次に第2層のSingのときと同
様にして、第4層として50nmの厚みのSiO2を被
覆し放電を停止した。最後にアルボッ20体積%、酸素
80体積%の混合ガスに真空槽内の雰囲気をほぼ完全に
置換し、0.4Paの圧力で硼酸ジルコニウムターゲッ
トに6 W / aa 2の電力を印加し、所定時間ス
パッタをおこない、40nmの厚みの透明なZrB、O
,なる組成の膜を被覆し、放電およびガスを停止してガ
ラス上に5層からなる膜が被覆された熱線反射性能を有
するサンプル18を得た。同様の方法により、層の厚み
、ガラス板の種類を変えてサンプル19〜20を得た。A power of 3 W/(J" was applied to the titanium target, sputtering was performed for a predetermined time, and 1100 nm was deposited on the glass.
TiO□ was coated as a first layer with a thickness of 2, and the discharge was stopped. The atmosphere in the vacuum chamber was almost completely replaced with 40% by volume of Albod and 60% by volume of oxygen, the pressure was set to 0.4Pa, a power of 5W/σ2 was applied to the silicon target, and sputtering was performed for a predetermined period of time to achieve a thickness of 200nm. SiO□ was coated as a second layer, and the discharge was stopped. After that, the cloud atmosphere was almost completely replaced with 50% by volume of Albod and 50% by volume of oxygen,
The pressure was adjusted to 0.4 Pa. A power of 5 W/cm'' was applied to the titanium target, sputtering was performed for a predetermined period of time, TiO□ was coated as a third layer of 1100 nm, and the discharge was stopped.Next, in the same manner as in the second layer Sing, The discharge was stopped by coating SiO2 with a thickness of 50 nm as the fourth layer.Finally, the atmosphere in the vacuum chamber was almost completely replaced with a mixed gas of 20 vol% Albot and 80 vol% oxygen, and a pressure of 0.4 Pa was applied. A power of 6 W/aa2 was applied to the zirconium borate target and sputtering was performed for a predetermined time to form a transparent ZrB, O with a thickness of 40 nm.
Sample 18 having a heat ray reflective property in which a five-layer film was coated on glass was obtained by stopping the discharge and gas. Samples 19 to 20 were obtained in the same manner by changing the layer thickness and the type of glass plate.
得られたサンプル18〜20の膜構成を第7表に光学特
性、酸およびアルカリに対する耐久性および耐摩耗性能
を調べた結果を第8表に示す。Table 7 shows the film structure of Samples 18 to 20 obtained, and Table 8 shows the results of examining optical properties, durability against acids and alkalis, and abrasion resistance.
比較例1
最上層に硼化ジルコニウムと酸素との反応生成物からな
る保護層を設けない実施例1の比較サンプルとして、ブ
ロンズ着色フロートガラスに第1層として65nmの厚
みのSnO2、さらに50nmの厚みのTiQz、さら
に50nmの厚みのSnO,を実施例1のサンプルと同
様の方法で順次被覆して比較サンプル1を得た。このサ
ンプルの膜構成を第1表に、耐久性能を第2表に示す。Comparative Example 1 As a comparative sample of Example 1 in which the uppermost layer is not provided with a protective layer made of a reaction product of zirconium boride and oxygen, bronze-colored float glass is coated with SnO2 having a thickness of 65 nm as the first layer and further having a thickness of 50 nm. Comparative sample 1 was obtained by sequentially coating TiQz with a thickness of 50 nm and SnO with a thickness of 50 nm in the same manner as the sample of Example 1. The membrane structure of this sample is shown in Table 1, and the durability performance is shown in Table 2.
比較例2
最上層に硼化ジルコニウムと酸素ガスとの反応生成物か
らなる保護層を設けない実施例2の比較サンプルとして
、ブロンズ着色フロートガラスに第1層として50nm
のTi0z、第2層として4nmの厚みの窒化ジルコニ
ウムを、実施例2のサンプルと同様の方法で順次被覆し
て比較サンプル2を得た。このサンプルの115W構成
を第3表に、耐久性能を第4表に示す。Comparative Example 2 As a comparative sample of Example 2 in which a protective layer made of a reaction product of zirconium boride and oxygen gas was not provided on the top layer, a 50 nm first layer was applied to bronze-colored float glass.
Comparative sample 2 was obtained by sequentially coating TiOz and zirconium nitride with a thickness of 4 nm as a second layer in the same manner as the sample of Example 2. The 115W configuration of this sample is shown in Table 3, and the durability performance is shown in Table 4.
比較例3
最上層に硼化ジルコニウムと酸素ガスとの反応生成物か
らなる保護層を設けない実施例3の比較サンプルとして
、ブロンズ着色フロートガラス上に第1Nとして40n
mの厚みのSnO2、さらに10nI11の厚みのTi
O2、さらに6nmの厚みの窒化チタニウム、さらに1
0nmの厚みのTi0z、さらに40rvの厚みのSn
O,を順次被覆して比較サンプル3を得た。このサンプ
ルの膜構成を第5表に、耐久性能を第6表に示す。Comparative Example 3 As a comparative sample of Example 3 in which a protective layer made of a reaction product of zirconium boride and oxygen gas was not provided on the top layer, 40n of 1N was applied on bronze colored float glass.
m thickness of SnO2, further 10nI11 thickness of Ti
O2, further 6 nm thick titanium nitride, further 1
TiOz with a thickness of 0nm, and Sn with a thickness of 40rv.
Comparative sample 3 was obtained by sequentially coating O. The membrane structure of this sample is shown in Table 5, and the durability performance is shown in Table 6.
比較例4
最上層に硼化ジルコニウムと酸素との反応生成物からな
る保護層を設けない実施例4の比較サンプルとして、ブ
ロンズ着色フロートガラスに1100nの厚みのTie
、、さらに200nmの厚みの5iOz、さらに100
r+mの厚みのTie2、さらに1100nの厚みの5
i02を順次被覆して比較サンプル4を得た。Comparative Example 4 As a comparative sample of Example 4 in which the top layer is not provided with a protective layer made of a reaction product of zirconium boride and oxygen, a Tie with a thickness of 1100 nm was prepared on bronze colored float glass.
,, further 200 nm thick 5iOz, further 100
Tie 2 with a thickness of r + m, and 5 with a thickness of 1100n
Comparative sample 4 was obtained by sequentially coating i02.
このサンプルの膜構成を第7表に、耐久性能を第8表に
示す。The membrane structure of this sample is shown in Table 7, and the durability performance is shown in Table 8.
第1表〜第8表に示すように、本発明にかかる最上層に
硼化ジルコニウムと酸素との反応生成物からなる保護層
を設けたサンプル1〜20は、いずれも前記保護層を設
けない比較サンプル1〜4よりも耐摩耗性能が優れてい
ることが分る。さらに得られたサンプル1〜20は、い
ずれも可視光線透過率が70%以上で、太陽光エネルギ
ーの遮へい性を示す日射透過率が70%以下で、窓ガラ
スとして明るい熱線遮へい性を有するガラスであること
が分る。さらに、サンプル1〜20は、使用したガラス
板との色調の差は、ΔX、ΔYが小さいことから透過色
、反射色について大きく変わらず、可視光線反射率が1
0%を越えないことから、窓ガラスとして外観がギラギ
ラした着色感がないことが分る。As shown in Tables 1 to 8, samples 1 to 20 according to the present invention in which a protective layer made of a reaction product of zirconium boride and oxygen is provided as the uppermost layer are not provided with the protective layer. It can be seen that the wear resistance performance is superior to that of Comparative Samples 1 to 4. Furthermore, the obtained samples 1 to 20 all have a visible light transmittance of 70% or more, a solar light transmittance that indicates solar energy shielding performance of 70% or less, and are bright glasses with heat ray shielding properties that can be used as window glass. I understand something. Furthermore, Samples 1 to 20 do not differ significantly in color tone from the glass plate used because ΔX and ΔY are small, and the transmitted color and reflected color do not differ significantly, and the visible light reflectance is 1.
Since it does not exceed 0%, it can be seen that the window glass does not have a shiny tinted appearance.
本発明にかかる熱線遮へいガラスは、最上層が耐摩耗強
度が強く、化学的に安定な硼化ジルコニウムの酸化物か
らなる保護層を有するため、実用に耐える摩耗強度をも
つ。したがって窓ガラスとして使用するにあたっては、
複層ガラスや合せガラスにする必要がなく膜面が直接外
気に触れる単板ガラスとして使用することができる。ま
た本発明の熱線遮へいガラスは、ガラス面からの可視光
線反射率が低く、かつ、太陽光のエネルギの一部を遮へ
いするので、自動車や建築物などの窓ガラスとして使用
するとき、ギラギラした感じを与えずに室内の冷房負荷
を低減することができる。The heat ray shielding glass according to the present invention has a protective layer that has a strong abrasion resistance and is made of a chemically stable oxide of zirconium boride, and therefore has an abrasion strength that is suitable for practical use. Therefore, when using it as window glass,
There is no need for double-glazed or laminated glass, and it can be used as a single-pane glass whose membrane surface is directly exposed to the outside air. In addition, the heat ray shielding glass of the present invention has a low reflectance of visible light from the glass surface and blocks part of the energy of sunlight, so when used as window glass for automobiles and buildings, there is no glare. It is possible to reduce the indoor cooling load without adding
第1図は本発明の熱線遮へいガラスの1実施例の一部断
面図である。
1・・・ガラス板、2・・・熱線遮へい性の被膜、3・
・・硼化ジルコニウムの酸化物からなる保護層1、〜’
jT1t’を亡−7FIG. 1 is a partial cross-sectional view of one embodiment of the heat ray shielding glass of the present invention. 1... Glass plate, 2... Heat ray shielding film, 3...
...Protective layer 1 made of oxide of zirconium boride, ~'
jT1t' death-7
Claims (1)
された熱線遮へい性の被膜と、前記被膜上に被覆された
硼化ジルコニウムの酸化物からなる保護層とからなる熱
線遮へいガラス 2)前記保護層の厚みが、5nm以上である特許請求範
囲第1項記載の熱線遮へいガラス3)前記保護層が、硼
化ジルコニウムのターゲットを減圧された酸化性ガスを
含む雰囲気中でスパッタリングすることにより被覆され
た、硼化ジルコニウムと酸化性ガスとの反応生成物であ
る第1項または第2項記載の熱線遮へいガラス 4)前記透明なガラス板の上に被覆された熱線遮へい性
の被膜が、ガラス板から数えて第1層として50〜70
nmの厚みのSnO_2、第2層として40〜65nm
の厚みのTiO_2が被覆された積層膜であって、前記
保護層の厚みが35〜70nmである特許請求範囲第1
項乃至第3項のいずれかの項記載の熱線遮へいガラス 5)10nmを越えない厚みの窒化チタニウム層が、前
記第1層のSnO_2と前記第2層のTiO_2との間
に設けられたことを特徴とする特許請求範囲第4項記載
の熱線遮へいガラス 6)40nmを越えない厚みのSnO_2層が、前記第
2層のTiO_2と前記保護層との間に設けられたこと
を特徴とする特許請求範囲第4項または第5項記載の熱
線遮へいガラス 7)前記透明なガラス板の上に被覆された熱線遮へい性
の被膜が、2〜10nmの厚みの窒化ジルコニウム層で
あって、前記保護層の厚みが5〜80nmである特許請
求範囲第1項乃至第3項のいずれかの項記載の熱線遮へ
いガラス 8)前記窒化ジルコニウム層に隣接してTiO_2層が
設けられ、前記隣接して設けられるTiO_2層が、前
記窒化ジルコニウム層と前記保護層との間に設けられる
ときは30nmを越えない厚みであり、前記透明なガラ
ス板と前記窒化ジルコニウム層との間に設けられるとき
は60nmを越えないことを特徴とする特許請求範囲第
7項記載の熱線遮へいガラス 9)前記透明なガラス板の上に被覆された熱線遮へい性
の被膜が、ガラス板側から数えて第1層として20〜6
0nmの厚みのSnO_2、第2層として2〜2nmの
厚みのTiO_2、第3層として2〜20nmの厚みの
窒化チタニウム、第4層として2〜20nmの厚みのT
iO_2が被覆された積層膜であって、前記保護層の厚
みが10〜80nmである特許請求範囲第1項乃至第3
項のいずれかの項記載の熱線遮へいガラス 10)前記第4層のTiO_2と前記保護層との間に、
60nmの厚みを越えないSnO_2層が設けられたこ
とを特徴とする特許請求範囲第9項記載の熱線遮へいガ
ラス 11)前記透明なガラス板の上に被覆された熱線遮へい
性の被膜が、ガラス板側から数えて第1層として80〜
130nmの厚みのTiO_2、第2層として160〜
230nmの厚みのSiO_2、第3層として80〜1
30nmの厚みのTiO_2、第4層として30〜80
nmの厚みのSiO_2が被覆された積層膜であって、
前記保護層の厚みが40〜80nmである特許請求範囲
第1項乃至第3項のいずれかの項記載の熱線遮へいガラ
ス 12)前記透明なガラス板がフロートガラスの板であっ
て、かつ、可視光線反射率が10%を越えない特許請求
範囲第4項乃至第11項のいずれかの項記載の熱線遮へ
いガラス[Scope of Claims] 1) A transparent glass plate, a heat ray-shielding coating coated on the transparent glass plate, and a protective layer made of zirconium boride oxide coated on the coating. 2) A heat ray shielding glass according to claim 1, wherein the protective layer has a thickness of 5 nm or more. 3) The protective layer contains an oxidizing gas obtained by reducing the pressure of a zirconium boride target. 4) The heat ray shielding glass according to item 1 or 2, which is a reaction product of zirconium boride and an oxidizing gas and is coated on the transparent glass plate by sputtering in an atmosphere. The heat ray shielding film is 50 to 70 as the first layer counting from the glass plate.
nm thick SnO_2, 40-65 nm as second layer
Claim 1 is a laminated film coated with TiO_2 with a thickness of , wherein the thickness of the protective layer is 35 to 70 nm.
5) A titanium nitride layer having a thickness not exceeding 10 nm is provided between the first layer of SnO_2 and the second layer of TiO_2. 6) A heat ray shielding glass according to claim 4, characterized in that a SnO_2 layer with a thickness not exceeding 40 nm is provided between the second layer of TiO_2 and the protective layer. Heat ray shielding glass according to range 4 or 5 7) The heat ray shielding film coated on the transparent glass plate is a zirconium nitride layer with a thickness of 2 to 10 nm, and the protective layer is 8) A TiO_2 layer is provided adjacent to the zirconium nitride layer, and the TiO_2 layer is provided adjacent to the zirconium nitride layer. When the layer is provided between the zirconium nitride layer and the protective layer, the thickness does not exceed 30 nm, and when the layer is provided between the transparent glass plate and the zirconium nitride layer, the thickness does not exceed 60 nm. 9) The heat ray shielding glass according to claim 7, characterized in that the heat ray shielding film coated on the transparent glass plate has a thickness of 20 to 6 as the first layer counted from the glass plate side.
SnO_2 with a thickness of 0 nm, TiO_2 with a thickness of 2-2 nm as the second layer, titanium nitride with a thickness of 2-20 nm as the third layer, T with a thickness of 2-20 nm as the fourth layer.
Claims 1 to 3 are laminated films coated with iO_2, wherein the protective layer has a thickness of 10 to 80 nm.
10) Between the fourth layer of TiO_2 and the protective layer,
11) The heat ray shielding glass according to claim 9, characterized in that a SnO_2 layer with a thickness not exceeding 60 nm is provided. 11) The heat ray shielding film coated on the transparent glass plate is 80~ as the first layer counting from the side
130 nm thick TiO_2, 160~ as second layer
230 nm thick SiO_2, 80~1 as third layer
30 nm thick TiO_2, 30-80 as the fourth layer
A laminated film coated with SiO_2 with a thickness of nm,
12) The heat ray shielding glass according to any one of claims 1 to 3, wherein the protective layer has a thickness of 40 to 80 nm. 12) The transparent glass plate is a float glass plate, and The heat ray shielding glass according to any one of claims 4 to 11, having a light reflectance not exceeding 10%.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP25129589A JPH03112833A (en) | 1989-09-27 | 1989-09-27 | Heat-ray shielding glass |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP25129589A JPH03112833A (en) | 1989-09-27 | 1989-09-27 | Heat-ray shielding glass |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH03112833A true JPH03112833A (en) | 1991-05-14 |
Family
ID=17220684
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP25129589A Pending JPH03112833A (en) | 1989-09-27 | 1989-09-27 | Heat-ray shielding glass |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH03112833A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0687923A3 (en) * | 1994-06-16 | 1996-07-17 | Kureha Chemical Ind Co Ltd | Infrared-blocking optical filter |
EP0738694A1 (en) * | 1995-04-18 | 1996-10-23 | SOCIETA' ITALIANA VETRO - SIV - S.p.A. | Process for the improvement of the abrasion resistance features and the chemical inertia of transparent thin coatings |
JP2012517396A (en) * | 2009-02-09 | 2012-08-02 | サン−ゴバン グラス フランス | Transparent glass body, manufacturing method thereof, and use thereof |
WO2016199676A1 (en) * | 2015-06-11 | 2016-12-15 | 旭硝子株式会社 | Film laminate and laminated glass |
-
1989
- 1989-09-27 JP JP25129589A patent/JPH03112833A/en active Pending
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0687923A3 (en) * | 1994-06-16 | 1996-07-17 | Kureha Chemical Ind Co Ltd | Infrared-blocking optical filter |
EP0738694A1 (en) * | 1995-04-18 | 1996-10-23 | SOCIETA' ITALIANA VETRO - SIV - S.p.A. | Process for the improvement of the abrasion resistance features and the chemical inertia of transparent thin coatings |
US5800684A (en) * | 1995-04-18 | 1998-09-01 | Societa Italiana Vetro - Siv - S.P.A. | Process for the improvement of the abrasion resistance features and of the chemical inertia of transparent thin coatings |
JP2012517396A (en) * | 2009-02-09 | 2012-08-02 | サン−ゴバン グラス フランス | Transparent glass body, manufacturing method thereof, and use thereof |
WO2016199676A1 (en) * | 2015-06-11 | 2016-12-15 | 旭硝子株式会社 | Film laminate and laminated glass |
JPWO2016199676A1 (en) * | 2015-06-11 | 2018-04-05 | 旭硝子株式会社 | Film laminate and laminated glass |
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