JPH09227164A - Reflection-reduced glass - Google Patents

Reflection-reduced glass

Info

Publication number
JPH09227164A
JPH09227164A JP8034503A JP3450396A JPH09227164A JP H09227164 A JPH09227164 A JP H09227164A JP 8034503 A JP8034503 A JP 8034503A JP 3450396 A JP3450396 A JP 3450396A JP H09227164 A JPH09227164 A JP H09227164A
Authority
JP
Japan
Prior art keywords
layer
glass
thin film
refractive index
film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP8034503A
Other languages
Japanese (ja)
Inventor
Kensuke Makita
研介 牧田
Atsushi Takamatsu
敦 高松
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Central Glass Co Ltd
Original Assignee
Central Glass Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Central Glass Co Ltd filed Critical Central Glass Co Ltd
Priority to JP8034503A priority Critical patent/JPH09227164A/en
Publication of JPH09227164A publication Critical patent/JPH09227164A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

PROBLEM TO BE SOLVED: To obtain a reflection-reduced glass bearing such functionally gradient characteristics as to gradually change the angle dependency of its reflection preventive characteristics from the above toward the below so as to improve the view-securing performance of the relevant driver. SOLUTION: This refection-reduced glass is obtained by providing at least one side of a transparent glass substrate with, as the 1st layer from the glass surface, a thin film layer 1.75-1.95 in refractive index (n1 ) with its thickness changed gradually within the range between 90 and 110nm followed by laminating the 1st layer with the 2nd thin film layer 2.1-2.3 in refractive index (n2 ) and 150-170nm in thickness and then laminating the 2nd layer with the 3rd thin film layer 1.4-1.5 in refractive index (n3 ) and 110-130nm in thickness.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【発明の属する技術分野】本発明は、主に車両等を運転
する際に、ことにダッシュボードもしくはこれらの周辺
部が特定傾斜角で取り付けたフロントガラスに対し、映
り込み現象ならびにギラツキ感が発現するのを入射角度
に対する依存性を少なくして低減させるようにし、ドラ
イバーの視界確保性能を高めることで、より安全性の向
上に寄与する反射低減ガラスに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention mainly shows a phenomenon of glare and a feeling of glare when driving a vehicle or the like, especially on a windshield mounted on a dashboard or a peripheral portion thereof at a specific inclination angle. The present invention relates to a reflection-reducing glass that contributes to further improvement in safety by reducing the dependency on the incident angle to reduce the dependency and improving the visibility securing performance of the driver.

【０００２】[0002]

【従来の技術】従来から、低反射ガラスならびに該範疇
に属するガラスが、各種提案がなされ実施されている。
ことに車両用窓ガラスにおいては、近年種々の機能性を
付与した高性能多機能ガラスが用いられるようになりつ
つあるとともに、車内の運転者や乗員はもとより対向車
等に対しても、より安全性を有し、居住性に優れかつ環
境に優しいものとなるものがより望まれつつあるなか
で、低反射ならびに該範疇に属する性能を有するガラス
が提案されてきている。2. Description of the Related Art Conventionally, various proposals have been made and implemented for low reflection glass and glass belonging to the category.
In particular, in window glass for vehicles, high-performance multi-function glass with various functionalities has been used in recent years, and it is safer not only for drivers and passengers in the vehicle but also for oncoming vehicles. Glasses having low reflectivity and performance belonging to the above category have been proposed, while glass having excellent properties, excellent habitability, and environmental friendliness has been more and more desired.

【０００３】特に、自動車窓のうち、特定傾斜角度で取
り付けたフロントガラスに用いた従来の低反射性能で
は、正面からの反射光の低減を目的としたものであり、
前記フロントガラス表面の垂直線（法線と以後いう）と
なす入射角が例えば50°〜70°以上の斜入射光に対して
は、その低反射効果が半減もしくはほとんどないもので
あって、例えば運転者がダッシュボードもしくはそれら
の周辺物がフロントガラスへの写り込みによって、ドラ
イビング時における前景の視認性が低下し、安全性の低
下等を発現することとなるものである。Particularly, in the conventional low reflection performance used for a windshield mounted at a specific inclination angle in an automobile window, the purpose is to reduce the reflected light from the front,
With respect to oblique incident light having an incident angle with the vertical line of the windshield surface (hereinafter referred to as a normal line) of, for example, 50 ° to 70 ° or more, its low reflection effect is halved or almost nonexistent. When the driver or the peripherals thereof are reflected on the windshield, the visibility of the foreground during driving is reduced, and the safety is reduced.

【０００４】これに対し、例えば特開平3-17601 号公報
には反射防止コーテイングの形成方法が記載されてお
り、軽金属酸化物プレカーサー、非水溶剤、および水を
含む反応性組成物のコーティングを基板上に形成し、十
分な時間加熱して濃縮し、該濃縮されたコーティング
を、弗素気体又は弗素生成気体状化合物を含む雰囲気
に、高められた温度で十分な時間さらして、該コーティ
ングの軽金属酸化物の酸素原子の少なくとも一部を、弗
素原子と置換することにより、コーティングの厚みに対
して軽金属弗化物の濃度勾配をもち、可視光の全スペク
トルに対して優れた反射防止性能を示すコーティングが
得られることとなるというものが開示されている。On the other hand, for example, Japanese Patent Application Laid-Open No. 3-17601 describes a method for forming an antireflection coating, in which a coating of a reactive composition containing a light metal oxide precursor, a non-aqueous solvent, and water is used as a substrate. Light metal oxidation of the coating formed above and concentrated by heating for a sufficient time and exposing the concentrated coating to an atmosphere containing fluorine gas or a fluorine-producing gaseous compound at elevated temperature for a sufficient time. By substituting at least a part of the oxygen atoms of the product with fluorine atoms, a coating having a concentration gradient of light metal fluoride with respect to the thickness of the coating and exhibiting excellent antireflection performance for the entire visible light spectrum can be obtained. What is to be obtained is disclosed.

【０００５】また、例えば特開昭64-70701号公報には導
電性反射防止膜を有する透明板が記載されており、導電
性付与の金属膜上に、屈折率が1.90〜2.50でかつ膜厚が
200Å〜400 Åの高屈折率誘電体膜と、該表面上に屈折
率が1.35〜1.50でかつ膜厚が700 Å〜1200Åの低屈折率
誘電体膜とからなるものが開示されている。Further, for example, Japanese Unexamined Patent Publication No. 64-70701 discloses a transparent plate having a conductive antireflection film, which has a refractive index of 1.90 to 2.50 and a film thickness on a metal film for imparting conductivity. But
A high refractive index dielectric film having a refractive index of 200Å to 400Å and a low refractive index dielectric film having a refractive index of 1.35 to 1.50 and a film thickness of 700Å to 1200Å are disclosed on the surface.

【０００６】また、例えば本出願人が既に出願した特開
平4-357134号公報に車両用反射低減ガラスを記載したよ
うに、ガラス面側から第１層として屈折率がn1＝1.8 〜
1.9でかつ膜厚が700 〜900 Åである薄膜層を被覆し、
次いで該第１層目薄膜層上に、第２層目として屈折率が
n2＝1.4 〜1.5 でかつ膜厚が1100〜1300Åである薄膜層
を被覆積層してなり、さらに前記表面の垂直線となす入
射角が50°〜70°の間で入射する膜面側の可視光に対
し、前記薄膜被覆積層面における反射率を通常の薄膜被
覆のないガラス面における反射率より4.5 〜6.5 ％低減
せしめて成るものを提案している。Further, for example, as described in Japanese Patent Application Laid-Open No. 4-357134, which has been filed by the applicant of the present invention, as a reflection-reducing glass for a vehicle, the refractive index n 1 = 1.8-
Covering a thin film layer having a thickness of 1.9 and a film thickness of 700 to 900Å,
Then, on the first thin film layer, a second layer having a refractive index of
n 2 = 1.4 to 1.5 and a film thickness of 1100 to 1300Å, which are laminated to form a film. It has been proposed that the reflectance of visible light on the laminated surface coated with the thin film is 4.5 to 6.5% lower than the reflectance on a glass surface not coated with the ordinary thin film.

【０００７】さらに、例えば特公昭47-1300 号公報には
安全フロントガラス、殊に自動車用の安全フロントガラ
スが記載されており、少なくとも１つのプラスチツク層
がガラス層の間に設けられており、かつ（または）少な
くとも１つのプラスチツク層がガラス層表面に設けられ
ている形式のものにおいて、フロントガラスの単数また
は複数のプラスチツク層の衝撃時の可撓性が鉛直方向で
変化しているものが開示されている。Further, for example, Japanese Patent Publication No. 47-1300 discloses a safety windshield, in particular for automobiles, in which at least one plastic layer is provided between the glass layers, and (Or) Disclosed is a type in which at least one plastic layer is provided on the surface of the glass layer, wherein the flexibility of the windshield or plastic layers upon impact changes in the vertical direction. ing.

【０００８】[0008]

【発明が解決しようとする課題】前述した例えば本出願
人が既に提案した特開平4-357134号公報に記載の車両用
反射低減ガラスでは、斜入射光に対する充分な反射低減
効果を発揮できるものとなるものの、入射角が 0〜40°
の光に対してその反射光の刺激純度が30％を超え最大約
35％程度となり、また入射角が50〜70°の光に対してそ
の反射光の刺激純度が20％を超える部分があって、最大
約21％程度となる等、必ずしもギラツキ感が低いものと
は言い難いものであった。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention In the above-mentioned vehicle reflection-reducing glass disclosed in, for example, Japanese Patent Application Laid-Open No. 4-357134, which is already proposed by the applicant of the present invention, a sufficient reflection-reducing effect for obliquely incident light can be exhibited. However, the incident angle is 0-40 °
The maximum stimulus purity of the reflected light exceeds 30% for the light of
It is about 35%, and there is a part where the stimulus purity of the reflected light exceeds 20% for light with an incident angle of 50 to 70 °, which is about 21% at the maximum. Was hard to say.

【０００９】また、例えば特公昭47-1300 号公報には安
全フロントガラス、殊に自動車用の安全フロントガラス
では、衝撃可撓性の変化を単数または複数のプラスチツ
ク層の鉛直方向（上下方向）での厚みの変化によってプ
ラスチツク層の強度をかえることで、ガラスに衝突する
乗員の頭部が下向きにねじれるようにし、安全性を高め
ようとするものであり、反射低減を念頭においたもので
はないし、単に層厚を変化させたからといって、反射低
減にはいたらない。Further, for example, Japanese Patent Publication No. 47-1300 discloses a safety windshield, particularly a safety windshield for automobiles, in which a change in impact flexibility is caused in the vertical direction (vertical direction) of one or more plastic layers. By changing the strength of the plastic layer according to the change in the thickness of the vehicle, the head of the occupant colliding with the glass is twisted downward so as to improve safety, and it is not intended to reduce reflection. Reflection reduction cannot be achieved simply by changing the layer thickness.

【００１０】現実の自動車でのダッシュボードのフロン
トガラスへの映り込みがあり、ダッシュボードのある１
点のドライバーの眼への映り込み角度は、ドライバーの
アイポイントより高いフロントウインドウの上部では小
さい角度となり、フロントウインドウの下部になるほど
大きい角度となり、このため最適には反射防止特性の角
度依存性が上部から下部に向かって徐々に変化する傾斜
特性になるように緩和せしめ、特に反射低減での一方方
向に傾斜特性をもたせることであり、前述した従来のも
のでは傾斜特性を考慮されておらず充分最適な反射低減
ガラスとは言い難い。There is a reflection of the dashboard on the windshield of a real car, and there is a dashboard 1
The angle of reflection of the dot on the driver's eye is smaller at the upper part of the front window, which is higher than the driver's eye point, and becomes larger at the lower part of the front window. This is to relax the slope characteristics so that it gradually changes from the upper part to the lower part, and in particular, to provide the slope characteristics in one direction by reducing reflection. It is hard to say that it is the optimum reflection reduction glass.

【００１１】[0011]

【課題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、透明ガラス基板の少
なくとも片側表面に形成した３層系の反射防止薄膜にお
いて、該薄膜の少なくとも１層目の膜厚を、鉛直方向に
対して所定の範囲で増加もしくは減少させることによっ
て、反射防止特性の角度依存性が上部から下部に向かっ
て徐々に変化するように緩和せしめた傾斜特性を付与す
るものであり、このガラスを用いて自動車用の合せガラ
スとすることによって、自動車のドライバーに対してダ
ッシュボードのフロントガラスへの映り込みによる運転
阻害を効果的に低減する等の有用な反射低減ガラスを提
供するものである。SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned drawbacks of the prior art, and is a three-layer antireflection thin film formed on at least one surface of a transparent glass substrate. By increasing or decreasing the film thickness of the first layer within a predetermined range with respect to the vertical direction, the tilt characteristic is relaxed so that the angle dependence of the antireflection characteristic gradually changes from the upper part to the lower part. By using this glass as a laminated glass for automobiles, it is useful reflection to effectively reduce driving hindrance due to reflection on the windshield of the dashboard for automobile drivers. A reduced glass is provided.

【００１２】すなわち、本発明は、透明ガラス基板の少
なくとも片側表面に、ガラス面側から第１層目として屈
折率がn1＝1.75〜1.95であってかつ膜厚が90〜110nm の
範囲で徐々に変化させた傾斜膜厚薄膜層を形成し、次い
で該第１層目の傾斜膜厚薄膜層上に、第２層目として屈
折率がn2＝2.1 〜2.3 であってかつ膜厚が150 〜170nm
である薄膜層を被覆積層し、さらに該第２層目の薄膜層
上に、第３層目として屈折率がn3＝1.4 〜1.5 であって
かつ膜厚が110 〜130nm である薄膜層を被覆積層して成
ることを特徴とする反射低減ガラス。That is, according to the present invention, on at least one surface of a transparent glass substrate, the first layer from the glass surface side has a refractive index n 1 = 1.75 to 1.95 and a film thickness of 90 to 110 nm gradually. Is formed on the first thin film layer having a gradient film thickness, and the second layer has a refractive index of n 2 = 2.1 to 2.3 and a film thickness of 150. ~ 170 nm
A thin film layer having a refractive index of n 3 = 1.4 to 1.5 and a film thickness of 110 to 130 nm as a third layer on the second thin film layer. A reflection-reducing glass which is formed by coating and laminating.

【００１３】ならびに、前記透明ガラス基板が、合せガ
ラスであることを特徴とする上述した反射低減ガラス。
さらに、前記合せガラスが、自動車用フロントウインド
ウであって、該ウインドウの車内側表面に、ガラス面側
から第１層目として屈折率がn1＝1.83〜1.87であってか
つ膜厚が下辺側において94nmで上辺側において108nm の
範囲で徐々に増加させた傾斜膜厚薄膜層を形成し、次い
で該第１層目の傾斜膜厚薄膜層上に、第２層目として屈
折率がn2＝2.17〜2.23でかつ膜厚が155 〜165nm である
薄膜層を被覆積層し、さらに該第２層目の薄膜層上に、
第３層目として屈折率がn3＝1.43〜1.47であってかつ膜
厚が115 〜125nm である薄膜層を被覆積層して成ること
を特徴とする上述した反射低減ガラスを提供するもので
ある。Further, the above-mentioned reflection-reducing glass, wherein the transparent glass substrate is a laminated glass.
Further, the laminated glass is a front window for an automobile, and a refractive index n 1 = 1.83 to 1.87 as a first layer from the glass surface side on the vehicle inner surface of the window and the film thickness is on the lower side. At 94 nm at the upper side, a thin film layer having a gradually increasing thickness is formed in the range of 108 nm on the upper side, and then the second film having a refractive index of n 2 = 2.17 to 2.23 and a film thickness of 155 to 165 nm is coated and laminated, and further on the second thin film layer,
The third layer is a reflection-reducing glass characterized by being formed by coating and laminating a thin film layer having a refractive index of n 3 = 1.43 to 1.47 and a film thickness of 115 to 125 nm. .

【００１４】[0014]

【発明の実施の形態】ここで、ガラス面側から第１層目
として屈折率がn1＝1.75〜1.95であってかつ膜厚が90〜
110nm の範囲で徐々に変化させた傾斜膜厚薄膜層を形成
し、次いで該第１層目の傾斜膜厚薄膜層上に、第２層目
として屈折率がn2＝2.1 〜2.3 であってかつ膜厚が150
〜170nm である薄膜層を被覆積層し さらに該第２層目
の薄膜層上に、第３層目として屈折率がn3＝1.4 〜1.5
であってかつ膜厚が110 〜130nm である薄膜層を被覆積
層して成ることとしたのは、２層膜の積層では反射色調
にわずかにギラツキ感が残存することもあるものであ
り、また４層以上の積層では高コストになるからであ
り、また第１、第２および第３層薄膜の前記屈折率なら
びに前記膜厚の値でなければ、前記表面の垂直線となす
入射角が20°〜70°の間で入射する膜面側の可視光に対
し、該薄膜被覆積層面における反射率が低減するだけで
なく、通常の薄膜被覆のないガラス面における反射率よ
り3.0 〜4.5 ％程度の低減となり、しかも反射防止特性
の角度依存性が上部から下部に向かって徐々に変化する
ように緩和せしめた傾斜特性を付与することができない
からである。BEST MODE FOR CARRYING OUT THE INVENTION Here, as the first layer from the glass surface side, the refractive index is n 1 = 1.75 to 1.95 and the film thickness is 90 to
A thin film layer having a gradient film thickness gradually changed in the range of 110 nm is formed, and then a second layer having a refractive index of n 2 = 2.1 to 2.3 is formed on the thin film film layer having a gradient film thickness of the first layer. And the film thickness is 150
A thin film layer having a thickness of up to 170 nm is laminated on the second thin film layer, and the third layer has a refractive index of n 3 = 1.4 to 1.5.
In addition, the reason why the thin film layer having a film thickness of 110 to 130 nm is coated and laminated is that the laminated film of the two-layer film may leave a slight glare in the reflection color tone. This is because a laminated structure of four or more layers is expensive, and if the refractive index and the film thickness of the first, second and third layer thin films are not the values, the incident angle with the vertical line of the surface is 20. For visible light incident on the film surface side between ° and 70 °, not only the reflectance on the thin film coated laminated surface is reduced, but also about 3.0 to 4.5% from the reflectance on the ordinary glass surface without the thin film coating. This is because it is not possible to provide a tilt characteristic in which the angle dependence of the antireflection characteristic is gradually changed from the upper portion to the lower portion.

【００１５】上述した膜構成により、ほとんど運転者等
に対し前記映り出しがなくなって映り出しを視認されに
くくなりかつ気にならなくなって、透視性を高めより安
全性に優れるものとなる。さらに運転者はもちろん同乗
者ならびに対向車の人等の環境に対して、特に必ずしも
人等の環境は特定の角度でガラスを見るとは限らず全て
の方角からの視認に対してよりギラツキ感を抑え、目や
身体の疲労の低減ならびにそれらによる不安全性を解消
し、人的物的両面から優しいものとなる。With the above-described film structure, the driver hardly sees the projection, and the projection is hardly visible and does not bother the driver, so that the transparency is improved and the safety is further improved. Furthermore, not only the driver, but also the passengers and the people in the oncoming vehicle, especially the environment such as people, does not always look at the glass at a specific angle, and the feeling of glare becomes more visible from all directions. It suppresses and reduces fatigue of eyes and body and eliminates the insecurity caused by them, and becomes gentle from both a human and physical standpoint.

【００１６】また、膜厚が鉛直方向に対して徐々に変化
する傾斜膜厚薄膜層については、少なくとも１種以上の
有機金属化合物もしくはその加水分解物と溶媒とを含む
溶液を用いるゾルゲルコーティングであり、ガラス基板
の片面のみに、溶液をガラス基板上部から流下させる所
謂ノズルフローコート法で光学薄膜を形成する。The thin film layer having a gradient film thickness whose thickness gradually changes in the vertical direction is a sol-gel coating using a solution containing at least one or more organic metal compounds or their hydrolysates and a solvent. An optical thin film is formed on only one surface of the glass substrate by a so-called nozzle flow coating method in which the solution is allowed to flow down from the upper portion of the glass substrate.

【００１７】さらに、前記第１層目薄膜層の薄膜が、Si
O2、TiO2、ZrO2、Al2O3 、B2O3のうちの２種以上を混合
したものから成ることが好ましく、屈折率が比較的高い
TiO2（2.20程度）、ZrO2（1.95程度）と屈折率が比較的
低いSiO2（1.45程度）、Al2O 3 （1.65程度）、B2O3（1.
60程度）とを種々組み合わせて混合することで、自由に
コントロールして屈折率が1.75〜1.95になるような複合
膜を得易く、かつ耐久性に優れるものとなるからであ
る。Further, the thin film of the first thin film layer is Si
OTwo, TiOTwo, ZrOTwo, AlTwoOThree, BTwoOThreeMix two or more of
It has a relatively high refractive index.
TiOTwo(About 2.20), ZrOTwo(About 1.95) and the refractive index is relatively
Low SiOTwo(About 1.45), AlTwoO Three(About 1.65), BTwoOThree(1.
About 60) can be mixed and mixed freely,
Controlled composite with refractive index of 1.75 to 1.95
Because it is easy to obtain a film and has excellent durability.
You.

【００１８】さらにまた、特に例えば第１層目薄膜層と
してモル比でTiO2：SiO2＝50：50〜60：40である薄膜
を、第２層目薄膜層としてTiO2薄膜を、第３層目薄膜層
としてSiO2薄膜を適宜組み合わせることが好ましく、前
記各成分の組み合わせの中でも、アルコキシドが安定で
成膜性がよく、均質な膜を得易く、最も優れた反射率低
減効果が得られ、かつ高耐久性であるものとなる。Furthermore, in particular, for example, a thin film having a molar ratio of TiO 2 : SiO 2 = 50: 50 to 60:40 is used as the first thin film layer, and a TiO 2 thin film is used as the second thin film layer. It is preferable to appropriately combine SiO 2 thin films as the second thin film layer, and among the combinations of the above respective components, the alkoxide is stable and film forming properties are good, a uniform film is easily obtained, and the most excellent reflectance reduction effect is obtained. It also has high durability.

【００１９】また、前記合せガラスは、前記光学薄膜付
きガラスの非成膜面を他のガラス基板とポリビニルブチ
ラールなどの樹脂フイルムを介して接着させたものであ
り、前記合せガラスが自動車用フロントウインドウであ
れば、該ウインドウの車内側表面に、ガラス面側から第
１層目として屈折率がn1＝1.83〜1.87であってかつ膜厚
が下辺側において94nmで上辺側において108nm の範囲で
徐々に増加させた傾斜膜厚薄膜層を形成し、次いで該第
１層目の傾斜膜厚薄膜層上に、第２層目として屈折率が
n2＝2.17〜2.23でかつ膜厚が155 〜165nm である薄膜層
を被覆積層し、さらに該第２層目の薄膜層上に、第３層
目として屈折率がn3＝1.43〜1.47であってかつ膜厚が11
5 〜125nm である薄膜層を被覆積層して成る反射低減ガ
ラスとすることが好ましいものである。The laminated glass is obtained by adhering the non-film-forming surface of the glass with an optical thin film to another glass substrate via a resin film such as polyvinyl butyral, and the laminated glass is a front window for automobiles. Then, on the car interior surface of the window, the refractive index is n 1 = 1.83 to 1.87 as the first layer from the glass surface side, and the film thickness is gradually increased in the range of 94 nm on the lower side and 108 nm on the upper side. To form a thin film layer having a gradient film thickness that is increased to the above, and then a second layer having a refractive index of
n 2 = 1.27 to 2.23 and a film thickness of 155 to 165 nm is coated and laminated, and the second thin film layer has a refractive index of n 3 = 1.43 to 1.47 as a third layer. It is and the film thickness is 11
It is preferable to use a reflection-reducing glass obtained by coating and laminating a thin film layer having a thickness of 5 to 125 nm.

【００２０】さらにまた、ガラス基板としては、透明ガ
ラスであれば無色あるいは有色のどちらでもよい、すな
わち例えばブルー、ブロンズ、グレーあるいはグリーン
ガラス等でもよく、特に自動車用窓材ではブルー色系あ
るいはゴールド色系、グリーン色系、なかでもゴールド
色系色調で熱線・紫外線吸収性能を得やすいものであれ
ばより好ましいものである。また単板で使用できること
はもとより、熱線反射ガラス、また複層あるいは合せガ
ラスあるいは強化ガラスまたは強度アップガラス、曲げ
ガラス等としても使用できることは言うまでもない。さ
らに、ガラス基板が無機質でも有機質でもよいことは言
うに及ばない。Furthermore, the glass substrate may be either colorless or colored, as long as it is transparent glass, that is, for example, blue, bronze, gray or green glass, etc., especially in automobile window materials, it is blue or gold. It is more preferable that the color tone is a system color, a green color color, and particularly a gold color tone, which easily obtains the heat ray / ultraviolet absorption performance. It goes without saying that it can be used not only as a single plate, but also as a heat ray reflective glass, a multi-layered or laminated glass, a strengthened glass, a strength-up glass, a bent glass and the like. Further, it goes without saying that the glass substrate may be inorganic or organic.

【００２１】前述したとおり、本発明の反射低減ガラス
は、中屈折率の薄膜と低屈折率の薄膜とした特定の屈折
率、ならびに所定の膜厚と特定範囲の膜厚で傾斜膜厚と
した薄膜を組み合わせ、シンプルな３層の薄膜被覆積層
にしたことにより、高い低反射性能を発揮し、またギラ
ツキ感もなく、前記表面の垂直線となす入射角が20°〜
70°の間で入射する膜面側の可視光に対し、該薄膜被覆
積層面における反射率が格段に低減でき、かつ通常の薄
膜被覆のないガラス面における反射率より3.0〜4.5 ％
程度の低減となり、しかも反射防止特性の角度依存性が
上部から下部に向かって徐々に変化するように緩和せし
めた傾斜特性を付与することができることとなる。As described above, the reflection-reducing glass of the present invention has a medium refractive index thin film and a low refractive index thin film having a specific refractive index, and a predetermined film thickness and a film thickness within a specific range to obtain an inclined film thickness. By combining thin films to form a simple 3-layer thin film coating laminate, high low reflection performance is exhibited, and there is no glare, and the incident angle with the vertical line of the surface is 20 ° ~
With respect to visible light incident on the film surface side between 70 °, the reflectance on the thin film-coated laminated surface can be significantly reduced, and is 3.0 to 4.5% than the reflectance on the ordinary glass surface without the thin film coating.
The degree of reduction can be reduced, and moreover, it is possible to provide the tilt characteristic in which the angle dependence of the antireflection characteristic is gradually changed from the upper portion to the lower portion.

【００２２】これにより、車内外側から見た際のギラツ
キ感を抑えることができ、反射を抑制した分透視性が向
上し、誤認や違和感が発現しないようにでき、さらに高
耐久性であって運転者等の乗員ならびに人々の環境に優
しい、自動車用の窓材等として有用な反射低減ガラスと
なるものである。As a result, it is possible to suppress the glare when viewed from the inside and outside of the vehicle, improve the transparency due to the suppression of reflection, prevent misidentification and discomfort from appearing, and have high durability and driving. It is a reflection-reducing glass that is environmentally friendly to passengers and other people and is useful as a window material for automobiles.

【００２３】[0023]

【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。The present invention will be described below in detail with reference to examples. However, the present invention is not limited to such an embodiment.

【００２４】実施例１ 先ずSiのアルコキシドとTiのアルコキシドとを酸化物換
算のモル比が55：45となるように混合した混合アルコキ
シドに、酸化物換算の溶質濃度が約0.04wt％となるよう
イソプロピルアルコールと微量の水および酸触媒を加え
て約１時間程度攪拌してアルコキシド溶液を得た。この
溶液の粘度は約2.5cP であった。この溶液を洗瓶に入れ
成膜用溶液とした。 Example 1 First, a mixed alkoxide obtained by mixing Si alkoxide and Ti alkoxide at an oxide-equivalent molar ratio of 55:45 was prepared so that the oxide-equivalent solute concentration was about 0.04 wt%. Isopropyl alcohol, a trace amount of water and an acid catalyst were added and the mixture was stirred for about 1 hour to obtain an alkoxide solution. The viscosity of this solution was about 2.5 cP. This solution was put into a washing bottle to obtain a film-forming solution.

【００２５】次に温度約25℃、湿度約55％に保ったクリ
ーンルーム内において、縦が約１ｍ、横が約1.5 ｍ、厚
みが約２mmの自動車用のブロンズ色調系ガラス基板を、
水平からの角度（傾斜角）が約40°になるよう支持具に
立て掛け、洗瓶中の塗布溶液をガラスの上端部に沿って
一定圧力で流下させてガラス基板のほぼ片面全面に塗膜
を形成した。溶液が全て基板上を流下した後も、この塗
膜が充分乾燥するように約10分間そのままの状態で保持
し、さらにこのガラスを約270 ℃で約30分間キュアーリ
ングして第１層目のゲル膜を片面に形成した。Next, in a clean room kept at a temperature of about 25 ° C. and a humidity of about 55%, a bronze-tone glass substrate for an automobile having a length of about 1 m, a width of about 1.5 m, and a thickness of about 2 mm was prepared.
Lean against the support so that the angle (tilt angle) from the horizontal is about 40 °, and let the coating solution in the washing bottle flow down along the upper edge of the glass at a constant pressure to coat the coating on almost one side of the glass substrate. Formed. Even after all the solution has flowed down on the substrate, this coating film is kept for about 10 minutes so that it is sufficiently dried, and this glass is cured at about 270 ° C for about 30 minutes to prepare the first layer. A gel film was formed on one side.

【００２６】次いで、Tiのアルコキシドを酸化物換算濃
度が 0.5wt％になるようにi-PAで希釈し、この溶液中
に、前記の片面に塗膜を形成したガラス基板の非膜面側
をマスキングテ−プで覆い、静かに浸漬した後、約６mm
／sec の一定速度で静かに引き上げた。約２分間程度そ
のまま静置して塗膜を乾燥させた後、ガラスのマスキン
グテ−プを取り除き、第１層目と同様に約270 ℃で約30
分間程度キュアーリングして第２層目の薄膜を積層形成
した。Then, the alkoxide of Ti was diluted with i-PA so that the concentration in terms of oxide was 0.5 wt%, and the non-film surface side of the glass substrate having a coating film formed on one surface was diluted with this solution. Cover with a masking tape and gently soak, then about 6 mm
It was pulled up gently at a constant speed of / sec. After leaving it for about 2 minutes to dry the coating film, the masking tape on the glass is removed, and at about 270 ° C for about 30 minutes as in the first layer.
Curing was performed for about a minute to form a second thin film layer.

【００２７】さらに次いで、シリコンテトラエトキシド
を出発原料としこれを加水分解させた市販のシリカゾル
溶液をエタノールと酢酸エチルおよびノルマルプロパノ
ールの混合溶媒で 0.4wt％に希釈した。この溶液の粘度
を測定したところ約3.0cP であった。この溶液中に、前
記の片面に塗膜が形成されたガラス基板の非膜面側をマ
スキングテープで覆い静かに浸漬した後、約 4.5mm／秒
の一定速度で静かに引き上げた。引き上げが完了した後
約２分間そのまま静置し塗膜を乾燥させてガラスのマス
キングテープを取り除き、第１、２層目と同様約270 ℃
で約30分間キュアーリングして第３層目のゲル膜を形成
させた。Further, a commercially available silica sol solution obtained by hydrolyzing silicon tetraethoxide as a starting material was diluted with a mixed solvent of ethanol, ethyl acetate and normal propanol to 0.4 wt%. When the viscosity of this solution was measured, it was about 3.0 cP. In this solution, the non-film side of the glass substrate having a coating film formed on one side was covered with a masking tape and gently dipped, and then gently pulled up at a constant rate of about 4.5 mm / sec. After the pulling up is completed, the coating film is dried by allowing it to stand for about 2 minutes, and the glass masking tape is removed.
Curing was carried out for about 30 minutes to form a gel film of the third layer.

【００２８】さらに次いで得られた３層のゲル膜を積層
したガラス基板を、自動車用のフロントウインドウの形
状（上下幅が約75cm）に切断し、さらにこのフロント用
ブロンズガラスと、該ガラスと同一形状に切断した薄膜
が形成されていないクリアガラスとを膜面が外向きにな
るよう重ね合わせ、雰囲気温度を約650 ℃に保った焼成
炉中を膜面が上向きとなるように水平に保った状態で約
15分間通過させて自動車ガラスの形状になるよう曲げ焼
成をした。Further, the obtained glass substrate on which three layers of gel films were laminated was cut into the shape of an automobile front window (upper and lower width was about 75 cm), and this front bronze glass and the same glass as the front glass were cut. The cut glass and the clear glass on which the thin film was not formed were laid on top of each other so that the film surface faced outward, and kept horizontally so that the film surface faced upward in the firing furnace where the ambient temperature was maintained at about 650 ° C. About in state
It was allowed to pass for 15 minutes and then bent and fired so as to have the shape of automobile glass.

【００２９】この２枚のガラス板を充分に冷却した後、
ポリビニルブチラール樹脂フイルムを２枚のガラス板間
に挟持させてオートクレーブに入れて加圧加熱し、自動
車用フロント合せガラスを作製した。After sufficiently cooling the two glass plates,
A polyvinyl butyral resin film was sandwiched between two glass plates, placed in an autoclave and heated under pressure to produce a front laminated glass for automobiles.

【００３０】なお、合せ加工する前の膜付きガラス基板
を各成膜した時点等で抜き取り焼成された酸化物薄膜の
屈折率と膜厚をエリプソメーターで測定したところ、第
１層目は屈折率n1＝1.85で膜厚d1はガラス基板上端部か
ら約５cm下方で約108nm 、さらに約30〜35cm下方のガラ
ス中央部付近で約100nm 、上端部より約70cm下方の下端
部付近で約94nmであり、薄膜の膜厚が上端部から下端部
に向かってほぼ0.22nm／cm（22nm／100cm ）の割合で上
向きに増加する傾斜膜であった。また屈折率の値から第
１層目の薄膜は、焼成によって55SiO2・45TiO2系の酸化
物膜になっているものであった。The refractive index and the film thickness of the oxide thin film sampled and fired at the time of forming each film-formed glass substrate before the bonding process were measured by an ellipsometer, and the first layer had a refractive index. When n 1 = 1.85, the film thickness d 1 is about 108 nm about 5 cm below the upper end of the glass substrate, about 100 nm near the center of the glass about 30 to 35 cm below, and about 94 nm near the lower end about 70 cm below the upper end. That is, the film was a graded film in which the film thickness increased upward from the upper end to the lower end at a rate of approximately 0.22 nm / cm (22 nm / 100 cm 2). Further, from the value of the refractive index, the thin film of the first layer was an oxide film of 55SiO 2 · 45TiO 2 system by firing.

【００３１】続いて、第２、３層目についても同様な測
定を行ったところ、第２層目は屈折率n2＝2.20、膜厚d2
＝約160nm のTiO2膜で、第３層目は屈折率n3＝1.45、膜
厚d3＝約120nm のSiO2膜であった。Subsequently, the same measurement was carried out for the second and third layers, and the second layer had a refractive index n 2 = 2.20 and a film thickness d 2.
= A TiO 2 film with a thickness of about 160 nm, and the third layer was a SiO 2 film with a refractive index n 3 = 1.45 and a film thickness d 3 = about 120 nm.

【００３２】さらに得られた自動車用フロント合せガラ
スの光学特性を、薄膜が形成されていない通常のフロン
トガラスと比較して測定したところ、表１の結果が得ら
れており、ガラス板の上端部から下端部に向かって反射
防止特性の入射角依存性が徐々に変化する傾斜特性を示
した。Further, the optical characteristics of the obtained automobile front laminated glass were measured by comparing with those of an ordinary windshield having no thin film formed thereon, and the results shown in Table 1 were obtained. Shows a tilt characteristic in which the incident angle dependence of the antireflection characteristic gradually changes from the bottom to the lower end.

【００３３】[0033]

【表１】 [Table 1]

【００３４】[0034]

【発明の効果】以上詳述したように、本発明は特定した
屈折率ならびに膜厚の薄膜、特に傾斜膜厚薄膜層を組み
合わせ、シンプルな３層の薄膜被覆積層によって、フロ
ントガラスにおける可視光線透過率が70％以上を満たす
ようにして格段の反射低減をし、ギラツキ感もなく、か
つ20°〜70°の斜入射光での反射率を3.0 〜4.5 ％程度
低減し、しかも反射防止特性の角度依存性が上部から下
部に向かって徐々に変化するように緩和せしめた傾斜特
性を付与することができることとなるものとしたことに
より、ことにダッシュボードもしくはこれらの周辺部の
映り込み現象を低減し、ドライバーの透視性を高めて、
誤認あるいは眼の疲労等を防いで安全性を向上するもの
であり、どの方向から見てもギラツキ感が少ない人的物
的の両面に対してもまたその環境に対しても優しいもの
となり、幅広い分野において有用な反射低減ガラスを提
供できるものである。As described above in detail, according to the present invention, a thin film having a specified refractive index and film thickness, particularly a thin film layer having a gradient film thickness is combined, and a simple three-layer thin film coating lamination is used to transmit visible light in a windshield. The reflectance is significantly reduced by satisfying the ratio of 70% or more, there is no glaring feeling, the reflectance at oblique incident light of 20 ° to 70 ° is reduced by about 3.0 to 4.5%, and the antireflection characteristic is reduced. By reducing the angle dependency so that it gradually changes from the top to the bottom, it is possible to reduce the glare phenomenon on the dashboard or these peripheral parts. And increase the driver's transparency,
It improves safety by preventing misidentification or eye fatigue, etc. It has a small sense of glare from any direction, and it is friendly to both human and physical properties and to the environment, and has a wide range. It is possible to provide a reflection-reducing glass useful in the field.

Claims (3)

【特許請求の範囲】[Claims] 【請求項１】 透明ガラス基板の少なくとも片側表面
に、ガラス面側から第１層目として屈折率がn1＝1.75〜
1.95であってかつ膜厚が90〜110nm の範囲で徐々に変化
させた傾斜膜厚薄膜層を形成し、次いで該第１層目の傾
斜膜厚薄膜層上に、第２層目として屈折率がn2＝2.1 〜
2.3 であってかつ膜厚が150 〜170nm である薄膜層を被
覆積層し、さらに該第２層目の薄膜層上に、第３層目と
して屈折率がn3＝1.4 〜1.5 であってかつ膜厚が110 〜
130nm である薄膜層を被覆積層して成ることを特徴とす
る反射低減ガラス。1. A transparent glass substrate having a refractive index of n 1 = 1.75 to at least one surface as a first layer from the glass surface side.
A gradient thin film layer having a thickness of 1.95 and gradually changing in the range of 90 to 110 nm is formed, and then a refractive index as a second layer is formed on the first thin film gradient layer. Is n 2 = 2.1 ~
2.3, a thin film layer having a film thickness of 150 to 170 nm is coated and laminated, and the third thin film layer has a refractive index of n 3 = 1.4 to 1.5 as a third layer, and Film thickness 110 ~
A reflection-reducing glass characterized by being formed by coating and laminating a thin film layer having a thickness of 130 nm. 【請求項２】 前記透明ガラス基板が、合せガラスであ
ることを特徴とする請求項１記載の反射低減ガラス。2. The reflection reducing glass according to claim 1, wherein the transparent glass substrate is a laminated glass. 【請求項３】 前記合せガラスが、自動車用フロントウ
インドウであって、該ウインドウの車内側表面に、ガラ
ス面側から第１層目として屈折率がn1＝1.83〜1.87であ
ってかつ膜厚が下辺側において94nmで上辺側において10
8nm の範囲で徐々に増加させた傾斜膜厚薄膜層を形成
し、次いで該第１層目の傾斜膜厚薄膜層上に、第２層目
として屈折率がn2＝2.17〜2.23でかつ膜厚が155 〜165n
m である薄膜層を被覆積層し、さらに該第２層目の薄膜
層上に、第３層目として屈折率がn3＝1.43〜1.47であっ
てかつ膜厚が115 〜125nm である薄膜層を被覆積層して
成ることを特徴とする請求項２記載の反射低減ガラス。3. The laminated glass is a front window for an automobile, and a refractive index n 1 = 1.83 to 1.87 as a first layer from the glass surface side on the vehicle inner surface of the window, and a film thickness. Is 94 nm on the lower side and 10 on the upper side.
A thin film layer having a gradient film thickness gradually increased in the range of 8 nm is formed, and then a second layer having a refractive index of n 2 = 2.17 to 2.23 and a film is formed on the thin film film layer having a gradient film thickness of the first layer. Thickness is 155-165n
A thin film layer having a refractive index n 3 = 1.43 to 1.47 and a film thickness of 115 to 125 nm as a third layer is further laminated on the second thin film layer by coating. The reflection-reducing glass according to claim 2, which is formed by coating and laminating.
JP8034503A 1996-02-22 1996-02-22 Reflection-reduced glass Pending JPH09227164A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP8034503A JPH09227164A (en) 1996-02-22 1996-02-22 Reflection-reduced glass

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP8034503A JPH09227164A (en) 1996-02-22 1996-02-22 Reflection-reduced glass

Publications (1)

Publication Number Publication Date
JPH09227164A true JPH09227164A (en) 1997-09-02

Family

ID=12416068

Family Applications (1)

Application Number Title Priority Date Filing Date
JP8034503A Pending JPH09227164A (en) 1996-02-22 1996-02-22 Reflection-reduced glass

Country Status (1)

Country Link
JP (1) JPH09227164A (en)

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