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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