JPH03199139A - Single heat insulating glass sheet and colored glass thereof - Google Patents
Single heat insulating glass sheet and colored glass thereofInfo
- Publication number
- JPH03199139A JPH03199139A JP33916789A JP33916789A JPH03199139A JP H03199139 A JPH03199139 A JP H03199139A JP 33916789 A JP33916789 A JP 33916789A JP 33916789 A JP33916789 A JP 33916789A JP H03199139 A JPH03199139 A JP H03199139A
- Authority
- JP
- Japan
- Prior art keywords
- film
- layer
- glass
- insulating
- thickness
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011521 glass Substances 0.000 title claims abstract description 96
- 239000000758 substrate Substances 0.000 claims abstract description 28
- 238000004544 sputter deposition Methods 0.000 claims abstract description 15
- 238000012360 testing method Methods 0.000 claims description 16
- 238000005299 abrasion Methods 0.000 claims description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 7
- 239000010408 film Substances 0.000 abstract description 89
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 19
- 229910010421 TiNx Inorganic materials 0.000 abstract description 9
- 229910003087 TiOx Inorganic materials 0.000 abstract description 7
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- 239000010409 thin film Substances 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 51
- 235000019646 color tone Nutrition 0.000 description 16
- 239000000126 substance Substances 0.000 description 11
- 238000002834 transmittance Methods 0.000 description 10
- 239000012528 membrane Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000005357 flat glass Substances 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- 239000011651 chromium Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 150000004767 nitrides Chemical class 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- -1 H Ti Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000005340 laminated glass Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 101150000971 SUS3 gene Proteins 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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、冷暖房効果を向上させるようにするとともに
、比較的低い、例えば約50%前後以下の可視光透過率
を有するものであって、しかも耐薬品性および耐摩耗性
も優れた単板の断熱ガラス板ならびにその色ガラスに関
し、なかでもスパッタ法で成膜して成る、建築用単板熱
線反射ガラスまたはその色ガラスとして有用であること
はもちろん、特に車輌用断熱ガラスとしても有用であっ
て、ことにサンルーフ、サイドあるいはドア用窓ガラス
など可視光透過率が比較的低い車両用単板の断熱ガラス
またはガラス面倒から見てシルバー系色調を示す車両用
単板の断熱色ガラスとして有用である単板の断熱ガラス
板ならびに単板の断熱色ガラス板を提供するものである
。Detailed Description of the Invention [Industrial Field of Application] The present invention improves heating and cooling effects and has a relatively low visible light transmittance, for example, about 50% or less, Moreover, it relates to a single-panel insulating glass plate with excellent chemical resistance and abrasion resistance, and its colored glass, which is particularly useful as a single-panel heat-reflecting glass for construction or its colored glass formed by sputtering. Of course, it is also particularly useful as insulating glass for vehicles, and is particularly useful for single-pane insulating glass for vehicles with relatively low visible light transmittance, such as sunroof, side or door window glass. The present invention provides a single heat insulating glass plate and a single heat insulating colored glass plate useful as a single heat insulating colored glass for a vehicle.
[従来の技術]
近年、建築物の周辺環境との調和などの関係上、例えば
高層建築物では外面における反射の割合が高い高性能断
熱ガラスの採用が多くなってきており、その製法として
はCVD法、スパッタ法等があるが、反射色調を自由に
調節できて多品種の生産に適する製法としてはスパッタ
法が採用されつつあり、その用途は建築用に限らず車両
用にも広く拡大されつつあり、さらに単板のままで使用
しても耐候性、耐久性があるというものが提案されてき
ており、なかでもスパッタ法で成膜した建築用断熱ガラ
スとして透明基板にSUS/TiN II!等を形成す
ることでシルバー色系あるいはゴールド色系等を呈する
ものを得ようとすることが知られている0例えば特開昭
63−242948号公報には、熱線反射ガラスが記載
されており、ガラス基板表面に基板側から順に金属膜、
窒化物膜及び酸化物膜を積層して形成した層側表面の可
視光反射率20%以下の熱線反射ガラスが開示され、金
属膜としてCr、Ti、Z「、Hf、Ta、 Si及び
これらの合金、並びにステンレスのなかから選ばれたも
の、窒化物としてTi、 Zr、 Ta、 Cr、 H
fの窒化物及びこれらの複合窒化物のなかから選ばれた
もの、酸化物としてTi、 Cr、 Zr、 Si、
Al、 Hf、Ta、 Nbの酸化物及びこれらの複合
酸化物のなかから選ばれたものであり、具体的にはガラ
ス基板/クロム[/窒化チタン膜/酸化チタン膜、ある
いはガラス基板/ステンレス膜/窒化チタン膜/酸化チ
タン膜等のm*が記載され、どちらかと言えばシルバー
色を呈すると考えられるものが開示されている。また特
開昭64−14130号公報には、熱線反射ガラスが記
載されており、ガラス基板上に、基板側から順次窒化物
層(例えばTiN膜)、酸化物層(例えばTi02 、
Sn02等)、金属層(例えばS[IS 、 Ti、
Cr等)、酸化物層(例えばTin 2 、Sn02)
、あるいは基板側から順次例えばTi02層、TiN層
、TiO□層、SUS層、Ti02層をそれぞれ積層さ
せてなるガラス基板側反射色がゴールドを呈し、かつ膜
形成面側反射色がニュートラル系で、反射率が20%以
下であるというものが開示されている。さらに本出願人
が既に出願した特願平1−53567号では熱線反射ガ
ラス板を記載しており、例えばG / SUSNx /
T iNあるいはTiNx0y/TiO□の多層膜、
あるいはさらにTi02膜の表面にAl−5iNxOy
を積層した構成で、種々のシルバー色系色調となって単
板でも充分使用可能であるものを提案している。さらに
また特開昭63−247352号公報には、反応性スパ
ッタリングによる透明コーティングが記載されており、
基材、基材上のコーテイング膜およびコーティング上の
保fl1Mを含む構成のコートした物品であって、この
保護膜がアルミニウムおよびケイ素を含む合金であるタ
ーゲットを反応性ガス中、特に0層%がN2+02ガス
中の割合で10〜30%にあるなかでスパッタすること
により形成された反応生成物の無定形層を含む膜である
ことが記載され、具体的にはAl−5iRx (但しR
;例えば0.30□+0.7 N 2等反応ガス)の保
護膜とするものが開示されている。[Prior Art] In recent years, in order to harmonize with the surrounding environment of buildings, for example, high-performance insulating glass with a high proportion of reflection on the external surface has been increasingly used in high-rise buildings, and the manufacturing method for this is CVD. sputtering method, sputtering method, etc., but the sputtering method is being adopted as a manufacturing method that allows the reflective color tone to be freely adjusted and is suitable for the production of a wide variety of products, and its applications are being expanded not only to architecture but also to vehicles. Moreover, it has been proposed that it is weather resistant and durable even when used as a single sheet, and among them, SUS/TiN II! For example, Japanese Patent Application Laid-Open No. 63-242948 describes a heat ray reflective glass. A metal film is applied to the surface of the glass substrate in order from the substrate side.
A heat-reflecting glass with a visible light reflectance of 20% or less on the layer side surface formed by laminating a nitride film and an oxide film is disclosed, and the metal film includes Cr, Ti, Z', Hf, Ta, Si, and the like. Selected from alloys and stainless steel, nitrides such as Ti, Zr, Ta, Cr, H
Ti, Cr, Zr, Si, oxides selected from f nitrides and composite nitrides thereof;
It is selected from oxides of Al, Hf, Ta, Nb, and composite oxides thereof, specifically, glass substrate/chromium [/titanium nitride film/titanium oxide film, or glass substrate/stainless steel film]. /titanium nitride film/titanium oxide film, etc. are described, and those that are considered to have a rather silver color are disclosed. Furthermore, JP-A No. 64-14130 describes a heat ray reflective glass in which a nitride layer (e.g. TiN film), an oxide layer (e.g. Ti02,
Sn02, etc.), metal layers (e.g. S[IS, Ti,
Cr, etc.), oxide layer (e.g. Tin 2, Sn02)
, or a glass substrate formed by laminating, for example, a Ti02 layer, a TiN layer, a TiO□ layer, an SUS layer, and a Ti02 layer in order from the substrate side, the reflective color on the side of the glass substrate is gold, and the reflective color on the film forming side is neutral, It is disclosed that the reflectance is 20% or less. Furthermore, Japanese Patent Application No. 1-53567, which the present applicant has already filed, describes a heat ray reflective glass plate, for example, G/SUSNx/
Multilayer film of TiN or TiNx0y/TiO□,
Alternatively, Al-5iNxOy may be added to the surface of the Ti02 film.
We are proposing a laminated structure with various silver color tones that can be used even as a single plate. Furthermore, JP-A No. 63-247352 describes transparent coating by reactive sputtering,
A coated article comprising a substrate, a coating film on the substrate, and a protective film on the coating, wherein the protective film is an alloy containing aluminum and silicon, in a reactive gas, in particular a coating film containing 0% It is described that the film includes an amorphous layer of reaction products formed by sputtering in a proportion of 10 to 30% in N2+02 gas, and specifically, Al-5iRx (however, R
For example, a protective film of 0.30□+0.7 N 2 or other reactive gas) is disclosed.
[発明が解決しようとする問題点]
前述したような従来の例えば特開昭63−242948
号公報に記載のものはガラス側から見た際の可視光反射
率が大きくなりやすくかつ膜全体としての密着性あるい
は耐摩耗性、耐薬品性等においても必ずしも充分耐久性
があるものとは言い難いものであって、建築用単板の断
熱窓ガラスとしてさらに改善が望まれ、特に例えば自動
車用断熱窓ガラスのうち単板で用いるドアあるいはサイ
ドガラス等には必ずしも充分採用できるとは言い難いも
のであり、また特開昭64−14130号公報に記載の
ものは、sus sを多層膜の一つに用いているものの
ガラス面から見た際ゴールド色調を呈するものであって
、特にヘーズ値の変化ならびに耐薬品性において必ずし
も充分満足できるとは言い難いものであり、さらに特願
平1−53567号に記載のものは、前述の両公報に記
載されたものより、耐摩耗性、耐食性ならびに耐候耐久
性において数段優れるものであって建築用単板の熱線反
射ガラスとしては充分有用であると言えるが、車両用単
板の熱線反射ガラスとしてより長期的耐久性あるいは苛
酷な環境または条件においてはまだまだ充分に満足し得
るものとは必ずしも言い難いものであり、さらにまた特
開昭63−247352号公報に記載されたものは、最
外表面膜としての耐摩耗性ならびに耐薬品性においては
表面上向上するものの、膜を構成している積層膜全体と
しては耐候耐久性が必ずしも充分優れたものとは言い難
いものである。[Problems to be solved by the invention] The conventional method as described above, for example, Japanese Patent Application Laid-Open No. 63-242948
The material described in the publication tends to have a large visible light reflectance when viewed from the glass side, and the film as a whole does not necessarily have sufficient durability in terms of adhesion, abrasion resistance, chemical resistance, etc. Further improvement is desired as a single-pane insulating window glass for construction, and in particular, it cannot be said that it can be fully used for doors or side windows that use a single-pane insulating window glass for automobiles. In addition, the one described in JP-A-64-14130 uses SUS as one of the multilayer films, but exhibits a gold tone when viewed from the glass surface, and is particularly susceptible to changes in haze value. Furthermore, the product described in Japanese Patent Application No. 1-53567 has better abrasion resistance, corrosion resistance, and weather resistance than those described in both of the above-mentioned publications. Although it can be said to be quite useful as a heat-reflecting glass for architectural veneers, it still has much better long-term durability or in harsh environments or conditions as a heat-reflecting glass for vehicle veneers. However, it is difficult to say that the film is completely satisfactory, and the film described in JP-A-63-247352 does superficially improve the abrasion resistance and chemical resistance as the outermost surface film. However, the weather resistance and durability of the entire laminated film constituting the film cannot necessarily be said to be sufficiently excellent.
いずれにしても、車両用単板の断熱ガラスおよびその着
色ガラスとしては、断熱性能、耐摩耗性、耐薬品性なら
びに耐候耐久性などに充分優れ、しかも所望の長期に亙
る耐久性を充分有するものであるものとは言い難いもの
であった。In any case, the single-pane insulating glass for vehicles and its colored glass must have sufficient heat insulation performance, abrasion resistance, chemical resistance, weather resistance, etc., and have sufficient durability over the desired long term. It was difficult to say that it was.
[問題点を解決するための手段]
本発明は、従来のかかる欠点に鑑みてなしたものであっ
て、特定の膜厚を有する特定の薄膜をガラス表面側と最
外表面側に設け、少なくともsus膜あるいはSUSN
x @ならびにTiNx膜、さらにTiOx @を順次
それぞれ組み合わせることで、耐摩耗性、耐薬品性、耐
候耐久性をもち、冷暖房に効果的な単板の車両用窓ガラ
スとして満足して採用でき、しかもシルバー色系色調を
ガラス面で呈するようにできる単板の断熱ガラス板およ
びその色ガラスを提供するものである。[Means for Solving the Problems] The present invention has been made in view of the above drawbacks of the conventional art, and includes providing a specific thin film having a specific thickness on the glass surface side and the outermost surface side, and at least SUS membrane or SUSN
By sequentially combining x @, TiNx film, and TiOx @, it can be satisfactorily used as a single-panel vehicle window glass that has abrasion resistance, chemical resistance, weather resistance, and is effective for air conditioning and heating. To provide a single heat insulating glass plate capable of exhibiting a silver color tone on a glass surface and colored glass thereof.
すなわち、本発明は、透明ガラス基板の一表面に、ガラ
ス面より第1層および第5層として膜厚がそれぞれ10
0−1000人(7) SiOx:l: タハAl ・
SiOxll、第2層としT 5tlSあルイはSUS
Nx膜、第3層としてTiNx1l、第4層とし7Ti
Oxlllをそれぞれスパッタ法で成膜したことを特徴
とする単板の断熱ガラス板、ならびに透明ガラス基板の
一表面に、ガラス面より第1層として膜厚が100−3
00人のSiOxまたはAl・SiOx膜、第2層とし
て膜厚が50−100人のSUSあるいはSUSNx膜
、第3層として膜厚が200〜400人のTiNx膜、
第4層として膜厚が0〜200人のTi0xll、第5
層として膜厚が300−500人のSiOxまたはAl
・SiOx膜をそれぞれスパッタ法で成膜して成るガ
ラス面側から見た反射色調がシルバー色系であることを
特徴とする単板の断熱色ガラス板、さらに前記した単板
の断熱ガラス板ならびに単板の断熱色ガラス板において
、CS−10Fによる摩耗輪を用いたテーバー試験にて
、1000回回転後回転後ズ値の変化量が試験前に比し
5%以内であることを特徴とする単板の断熱ガラス板な
らびに単板の断熱色ガラス板をそれぞれ提供するもので
ある。That is, in the present invention, a first layer and a fifth layer are formed on one surface of a transparent glass substrate, each having a thickness of 10 mm from the glass surface.
0-1000 people (7) SiOx:l: TahaAl ・
SiOxll, second layer T 5tlS aluminum is SUS
Nx film, TiNx1l as the third layer, 7Ti as the fourth layer
A single heat insulating glass plate characterized by forming a film of Oxllll by sputtering method, and a transparent glass substrate having a film thickness of 100-3 as the first layer from the glass surface on one surface.
SiOx or Al/SiOx film with a thickness of 50-100 mm as the second layer, TiNx film with a thickness of 200-400 mm as the third layer,
The fourth layer is Ti0xll with a film thickness of 0 to 200 people, the fifth layer
SiOx or Al with a thickness of 300-500 mm as a layer
・Single heat insulating colored glass plate characterized in that the reflective color tone seen from the glass surface side is silverish, which is formed by depositing SiOx films by sputtering, and the above-mentioned single heat insulating glass plate; A single heat insulating colored glass plate is characterized by a change in Z value after 1000 rotations of within 5% compared to before the test in a Taber test using a CS-10F abrasion wheel. The present invention provides a single-pane insulating glass plate and a single-pane insulating colored glass plate.
ここで、前記したようにガラス面より第1層および第5
層として膜厚がそれぞれ100〜1000人のSiOx
またはAl・SiOx膜としたのは、透明基板と第3層
膜との間に発現する応力を緩和し膜の密着性を高める
ために透明基板の組成成分の一部であるSiOx (1
< x≦2)またはAl −SiOx(2くx≦ 7/
2)膜を用いることとし、また最外表層である第5層と
しても特に耐摩耗性、化学的耐久性を向上せしめるため
ならびに下層の各層における密着性に応力の発現等悪影
響を与えないためすなわち積層膜全体として各種耐久性
が充分向上せしめるため5jOxまたはAl・SiOx
膜を用いることとしたものであり、前述の効果を安定し
て確実に達成できしかも生産性も加味したなかでは膜厚
がそれぞれ100−1000人必要であり、ことに第5
層として好ましい膜厚は200〜800人程度であって
、より好ましくは250〜700人である。さらに低屈
折率の干渉層として、構成層の薄膜と干渉を発現するも
のの色調への寄与は少なく、中間層の構成であるSUS
,TiNx、Ti0Xの各層とマッチィングせしめてガ
ラス面側から見ての反射色調がスパッター膜を成膜する
前とほとんど変化しない中性色すなわち所謂シルバー色
系色調を呈することとなり、これまでの構成品に対し、
光学的な特性をほとんど変えずに、耐候耐久性能のみを
向上させることが可能となるため、とくにSiOxまた
はAl−SiOx層の膜厚を第1層として100〜30
0人、第5層として300〜500人とすることが最も
効果的であるためである。つぎに第2層としてSUSま
たは5LISNx膜を用いることとしたのは、密着力は
もちろん耐薬品性が金属膜のなかでは優れるものであり
、特にSUSNx (N 2 : Arが1:1−1:
0の割合における雰囲気でスパッタリング)膜の方がよ
りこの傾向が強く、ことに耐酸性が良化するものである
等、膜自身の強度が向上するものであり、またガラス面
側から見て反射色調がシルバー色系を発現せしめるた
めに必要であり、第3層としてのTiNx(0< x≦
1)膜、第4層としてのTiOx (0< x≦2)膜
と順次積層することによって、それぞれが作用し合って
密着性、膜の強度、耐候耐久性ならびに、干渉膜として
色調と可視光透過率の調整に役立つものであり、特に第
3ならびに4層については膜面側から見た色調のバリニ
ーシランを有するものとすることができるものである。Here, as mentioned above, the first layer and the fifth layer are placed from the glass surface.
SiOx with a film thickness of 100 to 1000 layers each
Alternatively, the Al/SiOx film was used in order to alleviate the stress developed between the transparent substrate and the third layer film and improve the adhesion of the film.
<x≦2) or Al-SiOx (2x≦7/
2) We decided to use a film, and also as the fifth layer, which is the outermost surface layer, in order to particularly improve wear resistance and chemical durability, and to avoid adverse effects such as the development of stress on the adhesion of the lower layers, i.e. In order to sufficiently improve various durability of the entire laminated film, 5jOx or Al/SiOx is used.
It was decided to use a membrane, and in order to achieve the above-mentioned effects stably and reliably, and taking productivity into consideration, the thickness of each membrane would require 100 to 1000 people.
The preferred thickness of the layer is about 200 to 800 people, more preferably 250 to 700 people. Furthermore, as an interference layer with a low refractive index, although it exhibits interference with the thin film of the constituent layers, it contributes little to the color tone, and the SUS, which is the structure of the intermediate layer,
, TiNx, and Ti0X, the reflected color tone seen from the glass surface side becomes a neutral color, that is, a so-called silver color tone, which is almost unchanged from before the sputtering film was formed. For,
Since it is possible to improve only the weather resistance and durability performance without changing the optical properties, it is especially possible to increase the film thickness of the SiOx or Al-SiOx layer as the first layer to 100 to 30%.
This is because it is most effective to have 0 people and 300 to 500 people as the fifth layer. Next, we decided to use SUS or 5LISNx film as the second layer because it has excellent adhesion and chemical resistance among metal films, especially SUSNx (N 2 : Ar ratio of 1:1-1:
This tendency is stronger for films sputtered in an atmosphere with a ratio of The color tone is silvery.
TiNx (0< x≦
1) By sequentially stacking the film and the TiOx (0< x≦2) film as the fourth layer, each interacts with each other to improve adhesion, film strength, weather resistance, and improve color tone and visible light as an interference film. This is useful for adjusting the transmittance, and in particular, the third and fourth layers can have Balinese silane that has a different color when viewed from the film surface side.
前述のこれら中間層の膜厚については第2層のSUSあ
るいはSUSNx膜が50−100人、第3層のTiN
x膜が200−400人、第4層のTiOx膜が0−2
00人にすることによって、耐摩耗性、耐薬品性ならび
に耐候耐久性等の膜全体の強度、さらには所望のシルバ
ー色系色調を生産性よく得るために必要で最も好ましい
ものである。Regarding the film thickness of these intermediate layers mentioned above, the second layer of SUS or SUSNx film is 50-100, and the third layer is TiN.
x film 200-400 people, 4th layer TiOx film 0-2 people
00 is necessary and most preferable in order to obtain the strength of the entire film such as abrasion resistance, chemical resistance, and weather resistance, and also to obtain the desired silver color tone with good productivity.
なお、透明ガラス基板としては無色または着色の無機質
あるいは有機質ガラス基板であれば、いずれも採用でき
ることは言うもでもない、また前記した単板の断熱ガラ
ス板およびその色ガラスが例えば複層ガラス、合せガラ
スなどに採用して差し支えないことも言うまでもない。It goes without saying that any colorless or colored inorganic or organic glass substrate can be used as the transparent glass substrate.Also, the above-mentioned single-pane insulating glass plate and its colored glass can be replaced with, for example, double-glazed glass or laminated glass. Needless to say, it can be used for glass, etc.
[作用]
前述したとおり、本発明の単板の断熱ガラス板およびそ
の色ガラスは、特定の膜厚を有する特定の薄膜をガラス
表面側と最外表面側に設け、少なくともSUSあるいは
SUSNx W4ならびにTiNx膜、さらにTiOx
膜を順次それぞれ組み合わせたことによって、比較的低
い例えば50%前後以下の可視光透過率であって、耐摩
耗性としてテーバー試験によるヘーズの変化量を5%以
下にすることかでき、しかも各層の膜間の密着性を高め
しめることとなり、酸あるいはアルカリ等による腐蝕性
を改善して耐薬品性が向上し、例えば従来施工時におけ
るコンクリート液による劣化、傷等の発生を防止するた
めのシートの貼付けが不要になるなど、耐候耐久性に優
れるものとなるとともに、生産性ならびに作業性等もよ
り向上するものであり、単板として充分採用できるもの
となり、さらに適度の干渉効果をもたらし、断熱機能を
有し、ガラス面側から見てシルバー色系色調を発現でき
て高い安全性と居住性を備えるものとなり、建築用窓ガ
ラスではもちろん、車両用窓ガラスとしてもサンルーフ
、サイドあるいはドア用ガラス、ことに上下などに稼動
さすような部分においても充分採用できる単板の断熱ガ
ラス板およびその色ガラスを提供できるものである。[Function] As described above, the single heat insulating glass plate of the present invention and its colored glass are provided with a specific thin film having a specific thickness on the glass surface side and the outermost surface side, and are made of at least SUS or SUSNx W4 and TiNx. membrane and further TiOx
By sequentially combining the films, it is possible to achieve a relatively low visible light transmittance of, for example, around 50% or less, and a change in haze measured by the Taber test for abrasion resistance to be 5% or less. This increases the adhesion between the membranes, improves corrosion resistance caused by acids or alkalis, and improves chemical resistance. Not only does it not require pasting, it has excellent weather resistance and durability, but it also improves productivity and workability, making it suitable for use as a veneer, providing a moderate interference effect, and improving heat insulation. It has a silver color tone when viewed from the glass side, and has high safety and livability.It can be used not only as architectural window glass, but also as vehicle window glass, such as sunroof, side or door glass. In particular, it is possible to provide a single heat insulating glass plate and its colored glass, which can be fully used in parts that move vertically or the like.
[実施例]
以下、実施例により本発明を具体的に説明する。ただし
本発明は係る実施例に限定されるものではない。[Example] Hereinafter, the present invention will be specifically explained with reference to Examples. However, the present invention is not limited to these embodiments.
実施例1
大きさ600X600 am2、厚さ6■の透明ガラス
基板(Ft6)を中性洗剤、水すすぎ、イソプロピルア
ルコールで順次洗浄し、乾燥した後、マグネトロン反応
スパッタリング装置の真空槽内にセットしであるSi0
2とSUSとTiのターゲットに対向して上方を往復で
きるようセットし、つぎに前記槽内を図示していない真
空ポンプで6
約5 X 10 Torrまで脱気した後、該真空槽内
に3
Arと02ガスを同量導入して真空度を約2×10To
rrに保持し、前記Si02のターゲットにRF電力約
2.5KWを印加し、02ガス(但し、Arと02ガス
の流量比は1:0から0:1の範囲にあればよい、〉に
よるRFマグネトロンスパッタ中を、前記SiO□ター
ゲット上方においてスピード約50m/sinで前記板
ガラスを搬送することによって約300人厚さの5iO
xfi膜を成膜した。前記SiOx膜の成膜が完了した
後、SiO□ターゲットへの印加を停止する。Example 1 A transparent glass substrate (Ft6) with a size of 600 x 600 am2 and a thickness of 6 cm was sequentially washed with a neutral detergent, rinsed with water, and isopropyl alcohol, dried, and then set in a vacuum chamber of a magnetron reaction sputtering device. Some Si0
2, SUS, and Ti targets so as to be able to reciprocate upwards. Next, the inside of the tank was degassed to about 5 x 10 Torr with a vacuum pump (not shown), and then 3 Introduce the same amount of Ar and 02 gas to reduce the vacuum to approximately 2×10To
rr, apply RF power of about 2.5 KW to the Si02 target, and apply RF with 02 gas (however, the flow rate ratio of Ar and 02 gas may be in the range of 1:0 to 0:1). By transporting the plate glass through magnetron sputtering above the SiO□ target at a speed of about 50 m/sin, a 5iO
An xfi film was formed. After the formation of the SiOx film is completed, the application to the SiO□ target is stopped.
つぎに前述のガラス基板を前記真空槽中に置いたまま、
SUSターゲットに約1.OKWを印加し、Arガスに
よるDCマグネトロンスパッタ中を、前記SUSターゲ
ット上方において約500 am/*inで前記ガラス
基板を搬送することにより約50人厚さのsus gを
成膜した。前記sus膜の成膜が完了した後、SUSタ
ーゲットへの印加を停止する。Next, with the glass substrate described above placed in the vacuum chamber,
Approximately 1. OKW was applied, and the glass substrate was transported above the SUS target at about 500 am/*in during DC magnetron sputtering using Ar gas to form a SUS G film with a thickness of about 50 mm. After the formation of the SUS film is completed, the application to the SUS target is stopped.
つぎに前述したガラス基板を前記真空槽中に置いたまま
、Tiターゲットに約2.OKWを印加し、N2ガスに
よるDCマグネトロン反応スパッタ中を、前記Tiター
ゲット上方において約225■/鵬inで前記ガラス基
板を搬送することにより約200人厚さのTiNx膜を
成膜した。前記TiNx膜の成膜が完了した後、Tiタ
ーゲットへの印加を停止する。Next, while the glass substrate mentioned above was placed in the vacuum chamber, a Ti target was placed on it for about 20 minutes. OKW was applied, and the glass substrate was transported above the Ti target at a rate of about 225 inches/inch during DC magnetron reaction sputtering using N2 gas, thereby forming a TiNx film with a thickness of about 200 mm. After the formation of the TiNx film is completed, the application to the Ti target is stopped.
ついで前述と同様にして約50重鵬/鵬inで前記ガラ
ス基板を搬送することにより約300人のSiOx膜を
成膜した。Then, in the same manner as described above, about 300 SiOx films were deposited by transporting the glass substrates at a rate of about 50 layers.
得られた4層膜を有する単板の断熱ガラス板について、
可視光透過率(380〜780nm)、可視光反射率(
380〜780r++s)ならびに日射透過率(340
〜1800nm)については340型自記分光光度計(
日立製作新製)とJISZ8722. JISR310
6ニヨー) 7それぞれその光学的特性を求めた。さら
にテーバー試験によるヘーズ(曇り具合)値については
、テーバ−試験機(MODEL 503. TYBER
社製)に膜面を上にした10cm角の試験片をセットし
、膜面に荷重500gのかかった摩耗輪(CS−10F
)が2ケ所で当たるようになっているもので、1000
回回転した後、ヘーズメータ−(日本重色工業製、ND
H−200)によって測定し、試験前の測定値と対比し
、その変化量すなわち差(ΔH)をもって曇価率で表わ
した数値である。Regarding the obtained single-pane insulating glass plate with the four-layer film,
Visible light transmittance (380-780nm), visible light reflectance (
380~780r++s) and solar transmittance (340r++s)
~1800nm) using a 340-type self-recording spectrophotometer (
Newly manufactured by Hitachi) and JISZ8722. JISR310
6) 7) The optical properties of each were determined. Furthermore, regarding the haze (cloudiness) value by the Taber test, please use the Taber test machine (MODEL 503. TYBER
A 10 cm square test piece with the membrane surface facing up was set in a wear ring (CS-10F) with a load of 500 g applied to the membrane surface.
) is hit in two places, 1000
After rotating the haze meter (manufactured by Nippon Heavy Industries, ND)
H-200), compared with the measured value before the test, and the amount of change, that is, the difference (ΔH), is the numerical value expressed as the haze value.
次に、耐薬品性のうち耐酸試験については、約60℃の
温度で0,15規定のHCI溶液中に試験片(10cs
X IOC厘)を約48時間浸漬した後、可視光透過率
ならびに反射率(膜面)を測定することによって膜の劣
化状態を見て判断したものであり、耐アルカリ試験につ
いては、約60’Cで0.15規定のNaOH溶液に前
記と同じ大きさの試験片を約48時間浸漬した後、前述
と同様の測定を行い、膜の劣化状態を見て判断したもの
であり、それぞれ○印は試験後の透過率と反射率の変化
が3%以下で外観上はとんど変化が見られなかったもの
、×印は同様の変化が5%以上で外観上の変化が明らか
に目立ったものであり、Δ印は同。Next, for the acid resistance test of chemical resistance, test pieces (10 cs
The deterioration state of the film was determined by measuring the visible light transmittance and reflectance (film surface) after soaking the film for about 48 hours. After immersing a test piece of the same size as above in a 0.15 N NaOH solution for about 48 hours, the same measurements as above were carried out, and the deterioration state of the membrane was judged. Marked with "X" means that the change in transmittance and reflectance after the test was 3% or less and no change in appearance was observed, and "x" indicates that the change in transmittance and reflectance after the test was 5% or more and the change in appearance was clearly noticeable. The Δ marks are the same.
様にした変化が3〜5%であって外観上前記の中間的な
変化のものである。なお建築用JIS案であるl規定の
1(CI、1規定のNaOH溶液中、常雇で6時間の浸
漬において変化がないことという条件でも試験を行った
。The change in appearance was 3 to 5%, which was an intermediate change in appearance. The test was also conducted under the condition that there should be no change after 6 hours of full-time immersion in NaOH solution of 1 (CI, 1 standard) according to the JIS draft for construction.
前述の各測定値については表1に示す通りであり、断熱
性に優れる等、より優れた居住性を示す光学的特性を有
し、耐摩耗性や耐食性を充分有し、耐候耐久性を向上し
たものとなり、単板の断熱ガラス板として有用なものと
なり、所期のめざすものが得られ、ガラス面から見た色
調としてはシルバー色系であった。なお前記建築用JI
S案による試験においてももちろん合格するものであっ
た。The above-mentioned measurement values are shown in Table 1, and it has optical properties that indicate better livability, such as excellent heat insulation, sufficient wear resistance and corrosion resistance, and improved weather resistance and durability. As a result, it became useful as a single heat insulating glass plate, and the desired result was obtained, and the color tone seen from the glass surface was silver-ish. In addition, the above-mentioned JI for construction
Of course, he passed the test based on Plan S.
実施例2
前記実施例1と同様の方法で行い、表1に示すように一
部膜厚のみ変え4層膜を得て、実施例1で示した測定法
等によって測定し、同様の評価手段で行い、その結果を
表1に示す。Example 2 A 4-layer film was obtained using the same method as in Example 1, with only some film thicknesses changed as shown in Table 1, and measured by the measuring method shown in Example 1, etc., and using the same evaluation method. The results are shown in Table 1.
実施例1と同様のものが得られた。A product similar to Example 1 was obtained.
実施例3
前記実施例1と同様の方法で行い、ただ第2層のみSU
S#からSUSNx Hに変え、すなわちSUS3
ターゲットを用い、真空度約2.5 X 10 Tor
r、N2ガス中、印加電力約2.5 KW、透明ガラス
基板の搬送スピード約600 gem/+inの条件に
より、約100人厚さのSUSNx膜を成膜した。Example 3 Performed in the same manner as in Example 1, except that only the second layer was SU
Change from S# to SUSNx H, that is, use SUS3 target, vacuum degree approximately 2.5 x 10 Tor
A SUSNx film with a thickness of about 100 mm was formed under the following conditions: r, N2 gas, applied power of about 2.5 KW, and transport speed of the transparent glass substrate of about 600 gem/+in.
得られた単板の断熱色ガラス板は、実施例1で示した測
定法等によって測定し、同様の評価手段で行い、その結
果は表1の通りであって、前述の各実施例と同様のもの
が得られ、色調もほぼ同色系となった。なお、SUSN
x #を第2層に用いたことにより、SUS膜を用いた
同様の膜ならびにその膜厚構成に比し優れたものであっ
た。The obtained veneer heat-insulating colored glass plate was measured by the measuring method shown in Example 1, etc., and the same evaluation method was used. The color tone was almost the same. In addition, SUSN
By using x# in the second layer, it was superior to a similar film using an SUS film and its film thickness structure.
実施例4
前記実施例1と同様の方法、測定、評価手段で行い、第
4層のみSiOx膜からAl・SiOx Mlに変え、
すなわちAl−5i合金(Al:5i=1=1)タ3
一ゲットを用い、真空度約2.5 XIOTorr、
0□ガス中、印加電力的2.5 KW、透明ガラス基板
の搬送スピード約20mm/sinの条件により、約3
00人厚さのAl・SiOx膜を戒膜した。Example 4 Performed using the same method, measurement, and evaluation means as in Example 1, except that only the fourth layer was changed from SiOx film to Al/SiOx Ml,
That is, using an Al-5i alloy (Al:5i=1=1) target, the degree of vacuum is about 2.5 XIO Torr,
In 0□ gas, the applied power is 2.5 KW, and the conveyance speed of the transparent glass substrate is about 20 mm/sin, about 3
An Al/SiOx film with a thickness of 0.00 mm was coated.
得られた単板の断熱色ガラス板は、前述の各実施例と同
様のものが得られ、色調もほぼ同色系となった。The obtained veneer heat-insulating colored glass plates were similar to those of the above-mentioned examples, and the color tone was almost the same.
実施例5
前記実施例1と同様の方法、測定、評価手段で行い、た
だ第3層の上面にTi0xllを酸膜挿入して5層膜と
したものである。すなわちTiターゲットを用い、真空
度とガスと印加電力を実施例4と同じで、透明ガラス基
板の搬送スピードを約5mm/winの条件により、約
200人厚さのTiOx膜を成膜した。Example 5 The same methods, measurements, and evaluation methods as in Example 1 were used, except that an acid film of TiOxll was inserted on the upper surface of the third layer to form a five-layer film. That is, a TiOx film having a thickness of approximately 200 mm was formed using a Ti target, using the same vacuum degree, gas, and applied power as in Example 4, and transporting the transparent glass substrate at a speed of approximately 5 mm/win.
得られた単板の断熱色ガラス板は、前述の各実施例と同
様のものが得られ、その色調もほぼ同色系となった。The obtained veneer heat-insulating colored glass plates were similar to those of the above-mentioned examples, and the color tones thereof were almost the same.
実施例6〜lO
前記各実施例と同様の方法で行い、表1に示すように5
層積層多層膜の各膜厚を得て、実施例1で示した測定法
等によって測定し、同様の評価手段で行い、その結果を
表1に示す。Examples 6 to 1O were carried out in the same manner as in each of the above Examples, and as shown in Table 1, 5
The thickness of each layer of the laminated multilayer film was obtained and measured by the measuring method shown in Example 1, etc., and the same evaluation method was used. The results are shown in Table 1.
得られた単板の断熱色ガラス板は、前述の各実施例と同
様のものが得られ、その色調もほぼ同色系となった。The obtained veneer heat-insulating colored glass plates were similar to those of the above-mentioned examples, and the color tones thereof were almost the same.
比較例1〜5
前記各実施例と同様の方法によって行い、表1に示すよ
うに2〜4層の積層多層膜およびその各膜厚を得て、実
施例1で示した測定法等によって測定し、同様の評価手
段で行い、その結果を表1に示す。Comparative Examples 1 to 5 The same method as in each of the above Examples was used to obtain 2 to 4 laminated multilayer films and their respective film thicknesses as shown in Table 1, and the results were measured by the measuring method shown in Example 1. The results were shown in Table 1.
得られた断熱色ガラスは、それぞれ実施例の単板の断熱
色ガラス板に比して耐摩耗性、耐薬品性等に劣り、単板
では車両用断熱色ガラスとしてはもちろん採用が困雛で
あり、建築用としても必ずしも優れた特性を有するもの
とは言い難いものであって採用し難いものであった。The obtained heat-insulating colored glass has inferior abrasion resistance and chemical resistance compared to the single-pane heat-insulating colored glass plates of the examples, and it is difficult to use the single-pane glass as heat-insulating colored glass for vehicles. However, it cannot be said that it necessarily has excellent characteristics even for architectural use, and it has been difficult to adopt it.
(以下−白子コ
ー」
[発明の効果]
以上前述したように、本発明は透明ガラス基板にスパッ
タ法で、特定の薄膜を特定の膜厚でガラス表面上側と最
外表面側に設け、少なくともSUSあるいはSUSNx
膜ならびにTiNx膜、さらにTiOx膜を順次それぞ
れ組み合わせて積層したことによって、比較的低い可視
光透過率であって、断熱性能を有し、耐摩耗性、耐食性
ならびに耐候耐久性に優れ、ガラス面から見てシルバー
色系の色調となり、複層あるいは合せガラスはもちろん
単板で車両用としても使用できる居住性のよい効果的で
有用な単板の断熱ガラス板およびその色ガラスを効率よ
く提供できるものである。(Hereinafter - Shirakoko) [Effects of the Invention] As described above, the present invention provides a transparent glass substrate with a specific thin film of a specific thickness on the upper and outermost surfaces of the glass surface by sputtering. Or SUSNx
By sequentially combining and laminating the film, TiNx film, and TiOx film, it has relatively low visible light transmittance, has heat insulation performance, and has excellent abrasion resistance, corrosion resistance, and weather resistance. We can efficiently provide effective and useful single-pane insulating glass sheets that have a silvery tone when viewed, can be used not only as double-layered or laminated glass, but also as single-pane glass for vehicles, with good livability, and colored glass. It is.
Claims (3)
および第5層として膜厚がそれぞれ100〜1000Å
のSiO_xまたはAl・SiO_x膜、第2層として
SUSあるいはSUSN_x膜、第3層としてTiN_
x膜、第4層としてTiO_x膜をそれぞれスパッタ法
で成膜したことを特徴とする単板の断熱ガラス板。(1) On one surface of a transparent glass substrate, the first layer and fifth layer are each 100 to 1000 Å thick from the glass surface.
SiO_x or Al/SiO_x film, SUS or SUSN_x film as the second layer, TiN_x as the third layer.
A single heat insulating glass plate characterized in that a TiO_x film is formed as a x film and a TiO_x film as a fourth layer by a sputtering method.
として膜厚が100〜300ÅのSiO_xまたはAl
・SiO_x膜、第2層として膜厚が50〜100Åの
SUSあるいはSUSN_x膜、第3層として膜厚が2
00〜400ÅのTiN_x膜、第4層として膜厚が0
〜200ÅのTiO_x膜、第5層として膜厚が300
〜500ÅのSiO_xまたはAl・SiO_x膜をそ
れぞれスパッタ法で成膜して成るガラス面側から見た反
射色調がシルバー色系であることを特徴とする単板の断
熱色ガラス板。(2) On one surface of the transparent glass substrate, SiO_x or Al with a thickness of 100 to 300 Å is applied as the first layer from the glass surface.
・SiO_x film, SUS or SUSN_x film with a film thickness of 50 to 100 Å as the second layer, and a film thickness of 2 Å as the third layer.
00-400 Å TiN_x film, film thickness 0 as the fourth layer
~200 Å TiO_x film, 300 Å film thickness as fifth layer
A single heat-insulating colored glass plate characterized in that the reflected color tone seen from the glass surface side is silver-colored, which is formed by forming a ~500 Å SiO_x or Al.SiO_x film by sputtering, respectively.
色ガラス板において、CS−10Fによる摩耗輪を用い
たテーバー試験にて、1000回回転後のベース値の変
化量が試験前に比し5%以内であることを特徴とする請
求項1ならびに2記載の単板の断熱ガラス板ならびに単
板の断熱色ガラス板。(3) In the Taber test using a CS-10F abrasion wheel, the amount of change in the base value after 1000 rotations was compared to that before the test for the above-mentioned veneer insulating glass plate and veneer insulating colored glass plate. 3. The veneer insulating glass plate and the veneer insulating colored glass plate according to claims 1 and 2, wherein the insulating veneer is within 5%.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP33916789A JPH064498B2 (en) | 1989-12-27 | 1989-12-27 | Insulated glass plate and its colored glass |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP33916789A JPH064498B2 (en) | 1989-12-27 | 1989-12-27 | Insulated glass plate and its colored glass |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH03199139A true JPH03199139A (en) | 1991-08-30 |
JPH064498B2 JPH064498B2 (en) | 1994-01-19 |
Family
ID=18324876
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP33916789A Expired - Lifetime JPH064498B2 (en) | 1989-12-27 | 1989-12-27 | Insulated glass plate and its colored glass |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH064498B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114933422A (en) * | 2022-05-17 | 2022-08-23 | 长兴旗滨节能玻璃有限公司 | Antireflection coated glass and preparation method thereof |
-
1989
- 1989-12-27 JP JP33916789A patent/JPH064498B2/en not_active Expired - Lifetime
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114933422A (en) * | 2022-05-17 | 2022-08-23 | 长兴旗滨节能玻璃有限公司 | Antireflection coated glass and preparation method thereof |
CN114933422B (en) * | 2022-05-17 | 2024-05-24 | 长兴旗滨节能玻璃有限公司 | Anti-reflection coated glass and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
JPH064498B2 (en) | 1994-01-19 |
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