JPH08143331A - Uv shielding glass - Google Patents

Uv shielding glass

Info

Publication number
JPH08143331A
JPH08143331A JP28826894A JP28826894A JPH08143331A JP H08143331 A JPH08143331 A JP H08143331A JP 28826894 A JP28826894 A JP 28826894A JP 28826894 A JP28826894 A JP 28826894A JP H08143331 A JPH08143331 A JP H08143331A
Authority
JP
Japan
Prior art keywords
film
ultraviolet
glass
polysilazane
coating
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
JP28826894A
Other languages
Japanese (ja)
Inventor
Takeshi Kondo
剛 近藤
Takako Honda
貴子 本田
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 JP28826894A priority Critical patent/JPH08143331A/en
Publication of JPH08143331A publication Critical patent/JPH08143331A/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3405Surface 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 organic materials

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)
  • Surface Treatment Of Glass (AREA)

Abstract

PURPOSE: To improve absorptivity for UV rays, scratching resistance, wear resistance, durability and chemical resistance by forming an inorg. UV-absorbing film on the surface of a transparent base body and further covering this film with a polysilazane mixture film. CONSTITUTION: A soln. for an UV-absorbing film of 1-20wt.% concn. is prepared by dissolving metallic soap zinc or cerium alkoxide compd. and 0.1-6wt.% oxide such as SiO2 and TiO2 in a diluting solvent. The obtd. soln. is applied on the surface of a transparent base body at 15-25 deg.C and 40-50RH% and dried by heating at >=150 deg.C for about 15min to obtain a UV-absorbing film comprising zinc oxide or cerium oxide film of 0.01-1.5μm thickness. Then a soln. containing 5-40wt.% polysilazane mixture is applied on the surface of the UV-absorbing film at 20-50RH% and dried and cured by heating at 100-400 deg.C for 10-90min to obtain a polysilazane mixture film having 0.1-3μm thickness.

Description

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

【0001】[0001]

【産業上の利用分野】本発明は、紫外線吸収性能が優れ
た無機質のコーティング膜で被覆した透明体であって、
種々の優れた特性を維持しつつ、さらに単板に使用した
際、より耐擦傷性、より耐摩耗性ならびに耐久性がある
ものとした紫外線遮蔽ガラスに関するものである。
FIELD OF THE INVENTION The present invention relates to a transparent body coated with an inorganic coating film having excellent ultraviolet absorption performance,
The present invention relates to an ultraviolet-shielding glass which has various scratch resistance, abrasion resistance and durability when used as a single plate while maintaining various excellent properties.

【0002】なかでもことに、単板の紫外線遮蔽ガラス
として各種窓材、例えばビルあるいは住宅、車両、船
舶、航空機、さらには種々のディスプレイ機器などに、
特に厳しい使用条件と環境にある自動車用窓ガラスにも
使用できるようになる有用な紫外線遮蔽ガラスである。
In particular, it is used as a single-plate ultraviolet shielding glass for various window materials such as buildings or houses, vehicles, ships, aircraft, and various display devices.
It is a useful UV-shielding glass that can be used even for automobile window glass under particularly severe conditions and environment.

【0003】[0003]

【従来の技術とその問題点】従来から一般にガラス基板
等透明体に紫外線吸収性を付与する処理方法としては次
のようなものがある。
2. Description of the Related Art Conventionally, there have been the following treatment methods for imparting ultraviolet absorption to a transparent material such as a glass substrate.

【0004】先ず透明体自体に紫外線吸収性化合物を混
入配合する方法、例えばガラス中に金属化合物を溶融添
加する各種ガラス組成物(例えば、特開昭52ー47812 号
公報)、あるいは樹脂フイルム中に紫外線吸収剤を分散
添加する各種樹脂フイルム(例えば、実開昭59ー17925
号公報)があるが、いずれも少量多品種生産には向か
ず、吸収波長が紫外/可視領域の境界(例えば400nm 付
近)に及ぶものは着色やフイルムのくもり等を発現し易
く、ことに無色にするにはひと工夫を必要とするもので
あって、コントロールが必ずしも容易であるとは言い難
いものである。
First, a method of mixing and blending an ultraviolet absorbing compound into the transparent body itself, for example, various glass compositions in which a metal compound is melted and added into glass (for example, JP-A-52-47812) or a resin film is used. Various resin films to which an ultraviolet absorber is dispersedly added (for example, Jitsukai Sho 59-17925)
However, none of them are suitable for low-volume, high-mix production, and those with absorption wavelengths that reach the boundary between the UV and visible regions (for example, around 400 nm) are liable to develop coloring and film fog, and are particularly colorless. It takes some effort to achieve this, and it is not always easy to control.

【0005】また、紫外線吸収性透明膜を透明体表面に
貼り合わせる方法、例えば、紫外線吸収剤を含有するポ
リビニールブチラール中間膜等を介して挟み込んだ合せ
ガラス(例えば、特開昭56ー32352 号公報)があるが、
樹脂フイルム単独の場合より耐薬品性、耐擦傷性、耐久
性、着色あるいはくもりが改善されるものの、板ガラス
を2枚以上使用するため形状対応性が悪く、かなり厚く
なって軽量化になり難いものである。
Also, a method of laminating an ultraviolet absorbing transparent film on the surface of a transparent body, for example, a laminated glass sandwiched by a polyvinyl butyral intermediate film containing an ultraviolet absorber (for example, JP-A-56-32352). Gazette),
Chemical resistance, scratch resistance, durability, coloration or cloudiness is improved compared to the case of resin film alone, but since it uses two or more sheet glasses, it is difficult to conform to shape and it is difficult to be considerably thick and lightweight. Is.

【0006】さらに、紫外線吸収性透明膜を透明体表面
に形成する方法、例えば、透明体である基材にスパッタ
などの気相成膜法(例えば、特開平4ー76083 号公報)
あるいはゾルゲルなどの液相成膜法(例えば、特開平4
ー97103 号公報) があるが、有機化合物は使用できず、
無機化合物が吸収ベースとなるため、紫外/可視領域の
境界(約400nm )まで充分シャープにカットできない
し、また成膜にともなう基板温度の上昇や焼成が不可欠
のため、耐熱性の基板にしか適用できない。さらに一般
的な紫外線吸収剤を多量に含む有機樹脂コーティング膜
のみでは、耐薬品性、耐擦傷性、耐久性が劣るものとな
る。
Further, a method for forming an ultraviolet absorbing transparent film on the surface of a transparent body, for example, a vapor phase film forming method such as sputtering on a transparent substrate (for example, Japanese Patent Laid-Open No. 4-76083).
Alternatively, a liquid phase film forming method such as sol-gel (for example, Japanese Patent Laid-Open No.
-No. 97103), but organic compounds cannot be used,
Since an inorganic compound serves as an absorption base, it cannot be cut sharply to the UV / visible region boundary (about 400 nm), and since it is essential to raise the substrate temperature and baking during film formation, it is applicable only to heat-resistant substrates. Can not. Further, only the organic resin coating film containing a large amount of a general ultraviolet absorber has poor chemical resistance, scratch resistance and durability.

【0007】またさらに例えば、特開平1-245201号公報
には、紫外線カットフイルターが記載されており、透明
基材の少なくとも片面に、酸化亜鉛からなる薄膜が設け
られていることが開示されている。
Further, for example, Japanese Patent Application Laid-Open No. 1-245201 describes an ultraviolet cut filter, and discloses that a thin film made of zinc oxide is provided on at least one surface of a transparent substrate. .

【0008】また例えば、特開平4-182327号公報には、
表面処理ガラス及びその製造方法が記載されており、基
体上に、ZnO を含有した膜厚0.5 μm以上の紫外線吸収
膜が設けられたもの、ならびに下地層としてSiO2膜また
はSiO2/TiO2膜を、オーバーコート膜としてSiO2/ZrO2
膜等を用いるものが開示されている。
Further, for example, in Japanese Patent Laid-Open No. 4-182327,
A surface-treated glass and a method for producing the same are described, in which a UV absorbing film containing ZnO and having a thickness of 0.5 μm or more is provided on a substrate, and a SiO 2 film or a SiO 2 / TiO 2 film as a base layer. As an overcoat film with SiO 2 / ZrO 2
Those using a film or the like are disclosed.

【0009】さらにまた例えば、特開平5-345642号公報
には、紫外線遮蔽ガラスが記載されており、ガラスの両
面又は片面に酸化亜鉛からなる紫外線遮蔽薄膜が形成さ
れ、該紫外線遮蔽膜の上にポリカルボシラン又はポリメ
タロカルボシランの有機溶媒溶液が塗布されさらに焼成
されてなる保護膜が形成されたことが開示されている。
Further, for example, Japanese Patent Application Laid-Open No. 5-345642 discloses an ultraviolet shielding glass, in which an ultraviolet shielding thin film made of zinc oxide is formed on both sides or one side of glass, and the ultraviolet shielding film is formed on the ultraviolet shielding film. It is disclosed that a protective film formed by applying an organic solvent solution of polycarbosilane or polymetallocarbosilane and then baking the solution is formed.

【0010】さらに例えば、特開平6-56479 号公報に
は、紫外線遮蔽膜および紫外線遮蔽ガラスが記載されて
おり、酸化亜鉛からなる酸化亜鉛膜と、シロキサン縮合
を有しかつ粒径0.1 μm 以下の酸化セリウム微粒子を分
散した保護膜とからなるものが開示されている。
Further, for example, Japanese Unexamined Patent Publication No. 6-56479 discloses an ultraviolet shielding film and an ultraviolet shielding glass, which has a zinc oxide film made of zinc oxide and siloxane condensation and has a particle size of 0.1 μm or less. What is comprised of a protective film in which cerium oxide fine particles are dispersed is disclosed.

【0011】さらに例えば、本出願人は既に出願した特
開平3-223111号公報では、被膜形成用薬液および該薬液
を使用した紫外線吸収ガラスを提案し、2-エチルヘキサ
ン酸亜鉛、脂肪酸を含む溶液を所定条件で酸化重合して
得られる被薄膜形成用薬液を、板ガラス面に塗膜して焼
成することにより成膜し、紫外線のみを選択的に吸収す
ることを可能にしたことを記載した。
Further, for example, in the Japanese Patent Application Laid-Open No. 3-223111 filed by the applicant of the present invention, a coating solution and a UV absorbing glass using the solution are proposed, and a solution containing zinc 2-ethylhexanoate and a fatty acid is proposed. It was described that a chemical liquid for forming a thin film obtained by oxidative polymerization under the above-mentioned conditions was coated on a plate glass surface and baked to form a film, and it was possible to selectively absorb only ultraviolet rays.

【0012】また例えば、本出願人は既に出願した特願
平5-266987号では、紫外線熱線遮断ウィンドウおよびそ
の製造方法を提案し、透明な基板上に基板側より第1層
として第1の透明誘電体膜、第2層として第1の透明誘
電体膜と異なる第2の透明誘電体膜、第3層として金属
または金属窒化物膜、第4層として第3の透明誘電体膜
を順次形成し積層膜としたことでなる紫外線熱線遮断ウ
ィンドウであって、第1の透明誘電体膜として酸化亜鉛
と酸化シリコンの混合膜を使用したものを記載した。
Further, for example, in the Japanese Patent Application No. 5-266987 filed by the applicant of the present invention, an ultraviolet heat ray blocking window and a method for manufacturing the same are proposed, and a first transparent layer is formed on the transparent substrate from the substrate side as the first layer. A dielectric film, a second transparent dielectric film different from the first transparent dielectric film as the second layer, a metal or metal nitride film as the third layer, and a third transparent dielectric film as the fourth layer. An ultraviolet heat ray shielding window formed by forming a laminated film, in which a mixed film of zinc oxide and silicon oxide is used as the first transparent dielectric film is described.

【0013】さらにまた例えば、特公平6-650 号公報に
は、酸化チタン・酸化セリウム複合系ゾルおよびこのゾ
ルから形成された透明薄膜が記載されており、水和酸化
チタンおよび水和酸化セリウムの分散液に過酸化水素を
加えて、該水和酸化チタンおよび水和酸化セリウムを分
解し、次いで得られた溶液を加熱する方法で製造した酸
化チタン・酸化セリウム複合系ゾル。ならびに酸化チタ
ン・酸化セリウム複合系微粒子を含む透明薄膜が開示さ
れている。
Further, for example, Japanese Patent Publication No. 6-650 discloses a titanium oxide / cerium oxide composite sol and a transparent thin film formed from this sol. A titanium oxide / cerium oxide composite sol produced by a method in which hydrogen peroxide is added to a dispersion to decompose the hydrated titanium oxide and the hydrated cerium oxide, and then the resulting solution is heated. A transparent thin film containing titanium oxide / cerium oxide composite fine particles is also disclosed.

【0014】さらにまた例えば、特開平6-192598号公報
には、紫外線吸収ガラスが記載されており、ガラス表面
に酸化亜鉛、酸化チタンおよび酸化セリウムのうち少な
くとも1種を主成分とする紫外線吸収膜が形成された紫
外線吸収ガラスにおいて、紫外線吸収膜とガラスとの間
に、紫外線吸収膜の屈折率とガラスの屈折率の中間の屈
折率を有し、かつ熱線反射性能を有する中間膜が形成さ
れたことが開示されている。
Further, for example, Japanese Patent Application Laid-Open No. 6-192598 discloses an ultraviolet absorbing glass, and an ultraviolet absorbing film containing at least one of zinc oxide, titanium oxide and cerium oxide as a main component on the glass surface. In the ultraviolet absorbing glass formed with, between the ultraviolet absorbing film and the glass, an intermediate film having a refractive index intermediate between the refractive index of the ultraviolet absorbing film and the refractive index of the glass, and having a heat ray reflection performance is formed. It is disclosed.

【0015】一方、従来から各種シラザンが種々の用途
に使用されており、なかでも所謂物品の表面改質に係わ
るものとしては次のようなものがある。例えば、特開平
1-138107号公報には、改質ポリシラザン、その製造方法
及びその用途が開示されており、ペルヒドロポリシラザ
ンを出発原料とする原料ポリシラザンと、溶剤としてオ
ルトキシレンと、充填剤として炭化珪素とからなる溶液
を調製し、SUS 基盤に塗布し成膜したものが記載されて
いる。
On the other hand, various kinds of silazanes have been conventionally used for various purposes, and among them, the following are related to so-called surface modification of articles. For example,
Japanese Patent No. 1-138107 discloses a modified polysilazane, a method for producing the same, and a use thereof. The raw material polysilazane having perhydropolysilazane as a starting material, orthoxylene as a solvent, and silicon carbide as a filler are disclosed. It describes a solution prepared, coated on a SUS substrate, and formed into a film.

【0016】また例えば、特開平5-311120号公報には、
紫外線遮蔽ガラス保護膜形成用組成物および紫外線遮蔽
ガラスが開示されており、ZnO あるいはTiO2等の紫外線
遮蔽膜により被覆されたガラスの面に、(SiH2 基のSi-H
結合の数) /( すべてのSi-H結合の数) =0.13〜0.45の
間にあり、数平均分子量が200 〜100,000 であるポリシ
ラザンを必須組成分として含有し、例えばキシレン等の
溶媒で希釈した保護膜形成用組成物を被覆してなる紫外
線遮蔽ガラスが記載されている。
Further, for example, in Japanese Patent Laid-Open No. 5-311120,
Disclosed are a composition for forming an ultraviolet-shielding glass protective film and an ultraviolet-shielding glass, and the surface of the glass coated with an ultraviolet-shielding film such as ZnO or TiO 2 (SiH 2 -based Si-H
(Number of bonds) / (Number of all Si-H bonds) = 0.13 to 0.45, containing polysilazane having a number average molecular weight of 200 to 100,000 as an essential component, and diluted with a solvent such as xylene. An ultraviolet-shielding glass coated with a protective film-forming composition is described.

【0017】さらに例えば、特開平5-310444号公報に
は、撥水性物品およびその製造方法が開示されており、
基材と、例えばSiH4ガスと希釈用N2ガスとO2ガスを基材
表面上で反応させて形成した二酸化珪素含有被膜と、こ
の被膜の表面に形成した例えばヘキサメチルジシラザン
等のポリシロキサンの窒素アナログあるいは含フッ素ジ
シラザン系である有機シラザン化合物からなる撥水層か
らなるものが記載されている。
Further, for example, Japanese Patent Application Laid-Open No. 5-310444 discloses a water repellent article and a method for producing the same.
A substrate, for example, a silicon dioxide-containing coating formed by reacting SiH 4 gas, N 2 gas for dilution, and O 2 gas on the surface of the substrate, and a poly-oxide such as hexamethyldisilazane formed on the surface of this coating. A water repellent layer composed of a nitrogen analog of siloxane or an organic silazane compound which is a fluorine-containing disilazane system is described.

【0018】さらに例えば、本出願人は既に出願した特
開平5-163174号公報では、車両用紫外線遮断ガラスを開
示しており、ガラス上に酸化亜鉛からなる紫外線遮断膜
が少なくとも1層以上形成され、外部に例えば少なくと
もCH3-Si結合を有する化合物/およびまたはSi-N結合を
有する化合物を塗布して形成する等のシリコンを含有す
る層が形成されているものを記載している。
Further, for example, Japanese Patent Application Laid-Open No. 5-163174 filed by the applicant of the present invention discloses an ultraviolet blocking glass for vehicles, in which at least one ultraviolet blocking film made of zinc oxide is formed on the glass. , A layer containing silicon, such as formed by coating a compound having at least CH 3 —Si bond and / or a compound having Si—N bond on the outside, is formed.

【0019】[0019]

【発明が解決しようとする問題点】前述したように、例
えば前記特開平1-245201号公報に記載の紫外線カットフ
イルターでは、紫外線カット状況もシャープとは言い難
く、しかも耐酸性や耐アルカリ性はもちろん耐擦傷性が
劣り、単板で自動車用窓材等外装用としては採用できな
いものである。
DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention As described above, for example, in the ultraviolet cut filter described in Japanese Patent Laid-Open No. 1-245201, it is difficult to say that the ultraviolet cut condition is sharp, and of course, acid resistance and alkali resistance are not required. Since it is inferior in scratch resistance, it cannot be used as an exterior material such as a window material for automobiles as a single plate.

【0020】また例えば、特開平4-182327号公報に記載
の表面処理ガラス及びその製造方法では、紫外線吸収能
はともかく、耐酸性や耐アルカリ性や耐擦傷性について
は結局紫外線吸収膜である厚さ1.5 μm 程度のZnO 厚膜
に対してSiO2薄膜またはSiO2/TiO2薄膜等の下地層を設
け、しかもSiO2/ZrO2薄膜またはZrO2/B2O3薄膜等のオ
ーバーコートが必ず必要となり、特に3層構成によって
良好となるものであり、コスト的に高く好ましいとは言
い難い。また全体の膜厚が厚くなり、焼成時においてク
ラックが発生し易くなる。
Further, for example, in the surface-treated glass and the method for producing the same described in Japanese Patent Laid-Open No. 4-182327, the UV absorbing ability is not included, but the thickness of the UV absorbing film is not the same for acid resistance, alkali resistance, and scratch resistance. An underlayer such as SiO 2 thin film or SiO 2 / TiO 2 thin film is provided for a ZnO thick film of about 1.5 μm, and an overcoat such as SiO 2 / ZrO 2 thin film or ZrO 2 / B 2 O 3 thin film is required. In particular, the three-layer structure is favorable, and it is difficult to say that it is preferable because of its high cost. In addition, the overall film thickness becomes thicker, and cracks are more likely to occur during firing.

【0021】さらにまた例えば、特開平5-345642号公報
に記載の紫外線遮蔽ガラスでは、酸化亜鉛膜の保護膜と
して、例えば高価であるポリカルボシランまたは該ポリ
カルボシランにSi、Ti、Zr、Al、B のアルコキシドを単
独もしくは複合して混合して用い、250 〜700 ℃で焼成
したとしても単板で自動車用窓材等外装用として充分耐
擦傷性や耐摩耗性を有しているとは言い難い。
Furthermore, for example, in the ultraviolet shielding glass disclosed in Japanese Patent Laid-Open No. 5-345642, as a protective film for a zinc oxide film, for example, expensive polycarbosilane or polycarbosilane containing Si, Ti, Zr, Al is used. , B alkoxides alone or in combination are used, and even if they are fired at 250 to 700 ° C, they are single plates and have sufficient scratch resistance and abrasion resistance as exterior materials such as automobile window materials. Hard to say.

【0022】また例えば、特開平6-56479 号公報に記載
の紫外線遮蔽膜および紫外線遮蔽ガラスでは、酸化亜鉛
膜の保護膜として、例えばシロキサン結合を有しかつ粒
径0.1 μm 以下の酸化セリウム微粒子を分散したものと
しても、膜厚が厚いため曲げ強化処理において、膜収縮
による基板ガラスの反りが大きい等、単板で自動車用窓
材等外装用として充分採用できるものとは言い難い。
Further, for example, in the ultraviolet shielding film and the ultraviolet shielding glass described in JP-A-6-56479, cerium oxide fine particles having a siloxane bond and having a particle diameter of 0.1 μm or less are used as a protective film for a zinc oxide film. Even if dispersed, it is hard to say that it is a single plate that can be sufficiently adopted as an exterior such as a window material for automobiles because the substrate glass is largely warped due to film shrinkage in the bending strengthening treatment due to its thick film thickness.

【0023】さらに例えば、本出願人は既に出願した特
開平3-223111号公報では、被膜形成用薬液および該薬液
を使用した紫外線吸収ガラスについては、ZnO 前駆体の
焼成(400 〜500 ℃)とオーバーコートのシリカ膜の焼
成(500 〜700 ℃)と2回の比較的高温焼成工程が必要
となり、エネルギーコストの増大を伴い、工程上から充
分改善されているとは言い難いものである。
Further, for example, in the Japanese Patent Application Laid-Open No. 3-223111 filed by the applicant of the present invention, the chemical liquid for forming a film and the ultraviolet absorbing glass using the chemical liquid are described as baking a ZnO precursor (400 to 500 ° C.). It is difficult to say that the overcoating silica film is baked (500 to 700 ° C.) and two relatively high temperature baking steps are required, and the energy cost is increased, and the steps are sufficiently improved.

【0024】また例えば、本出願人は既に出願した特願
平5-266987号では、紫外線熱線遮断ウィンドウおよびそ
の製造方法については、例えばスパッタ法とゾルゲル法
との併用であり、しかも4層コート積層膜であるため性
能的には良いものの、コスト上必ずしも好ましいもので
はない。
For example, in Japanese Patent Application No. 5-266987 filed by the applicant of the present invention, the ultraviolet heat ray shielding window and its manufacturing method are, for example, a combination of a sputter method and a sol-gel method, and a four-layer coating laminate. Since it is a film, the performance is good, but it is not always preferable in terms of cost.

【0025】さらにまた例えば、特公平6-650 号公報に
記載の酸化チタン・酸化セリウム複合系ゾルおよびこの
ゾルから形成された透明薄膜では、単板で自動車用窓材
等外装用として充分耐擦傷性や耐摩耗性を有している薄
膜を得ることはでき難い。
Furthermore, for example, in the titanium oxide / cerium oxide composite sol and the transparent thin film formed from this sol described in Japanese Patent Publication No. 6-650, a single plate is sufficiently scratch-resistant for exteriors such as automobile window materials. It is difficult to obtain a thin film that has abrasion resistance and abrasion resistance.

【0026】さらにまた例えば、特開平6-192598号公報
に記載の紫外線吸収ガラスでは、紫外線吸収率が必ずし
も充分とは言い難く、しかも可視光反射率が充分低減さ
れているものとは言い難くギラギラが若干見られるもの
である。
Furthermore, for example, in the ultraviolet absorbing glass described in Japanese Patent Laid-Open No. 6-192598, it is difficult to say that the ultraviolet absorptivity is always sufficient, and the visible light reflectance is not sufficiently reduced. Is a little seen.

【0027】いずれも、紫外線吸収性能ならびに耐摩耗
性や耐薬品性、耐候性等が従来に比し改善しようとして
いるものの、長期間の摺動接触等より過酷な使用条件あ
るいはより厳しい環境、例えばフロントガラスやリアガ
ラスや昇降するサイドドアガラスなどの自動車用窓ガラ
スとして種々の環境のなかで長期的に、例えば1年以上
さらに具体的には1〜5年程度の使用後に支障を生じる
ような傷や劣化がほとんど発現しないものとして安定使
用するには、充分確実なものとは必ずしも言い難い部分
もあるものであった。
In all cases, the ultraviolet absorption performance and the abrasion resistance, chemical resistance, weather resistance and the like are being improved as compared with the conventional ones, but the operating conditions are severer than the conventional ones such as long-term sliding contact, or more severe environment, for example, As a window glass for automobiles such as windshield, rear glass, and side door glass that moves up and down, scratches that cause troubles after being used for a long time in various environments, for example, for one year or more, more specifically for about 1 to 5 years. However, it is difficult to say that it is sufficiently reliable for stable use because it hardly causes deterioration.

【0028】一方、例えば前記特開平5-163174号公報に
記載の車両用紫外線遮断ガラスでは、確かに優れた紫外
線遮断性、あるいはウィンドウの昇降や引っ掻きやこす
りに対して優れた耐擦傷性あるいは耐候性を有するもの
となったものの、紫外線吸収膜の成膜と保護層の成膜と
2回の高温焼成をする必要があり、紫外線吸収膜への基
板からの影響を受け易く、コスト上または工程上からも
充分好ましいものは言い難く、しかも紫外線吸収膜を充
分厚いものとすると例えばクラック等も発現し易くな
る。その膜厚に制約があるようになるもので、結局所期
のめざす自動車用窓ガラス仕様に対応できるとは言い難
いものである。
On the other hand, for example, in the ultraviolet blocking glass for vehicles described in the above-mentioned Japanese Patent Laid-Open No. 5-163174, it is sure that the ultraviolet blocking property is excellent, or that it has excellent scratch resistance or weather resistance against window up / down and scratching or rubbing. However, since it is necessary to form the ultraviolet absorbing film, the protective layer, and the high temperature baking twice, the ultraviolet absorbing film is easily affected by the substrate, and the cost or the process is increased. From the above, it is difficult to say what is preferable, and when the ultraviolet absorbing film is made sufficiently thick, for example, cracks are likely to occur. Since the film thickness will be restricted, it is hard to say that it can meet the automotive window glass specifications aimed at the localizing period.

【0029】また、同様に例えば、前記特開平1-138107
号公報に記載の改質ポリシラザン、その製造方法及びそ
の用途では、必ずしも比較的低温硬化型のポリシラザン
混合物とは言い難く、しかも透明体のような充分な透視
性を要求されるものには採用できないものである。
Similarly, for example, the above-mentioned Japanese Patent Laid-Open No. 1-138107.
In the modified polysilazane, the method for producing the same and the use thereof described in Japanese Patent Publication, it cannot be said that it is a relatively low temperature-curable polysilazane mixture, and it cannot be adopted for a transparent body which requires sufficient transparency. It is a thing.

【0030】さらに、例えば前記特開平5-311120号公報
に記載の紫外線遮蔽ガラス保護膜形成用組成物および紫
外線遮蔽ガラスでは、必ずしも比較的低温硬化型のポリ
シラザン混合物とは同様に言い難く、上記したと同様な
こと等が発現し易いものである。
Further, for example, in the composition for forming an ultraviolet-shielding glass protective film and the ultraviolet-shielding glass described in JP-A-5-311120, it cannot be said that it is a relatively low temperature curing type polysilazane mixture. It is easy for the same thing as that to occur.

【0031】さらにまた、例えば特開平5-310444号公報
に記載の撥水性物品およびその製造方法では、二酸化珪
素被膜をガラス面での下地層にし、その上に有機シラザ
ン化合物をシラザン系撥水剤として被膜するものであっ
て、紫外線吸収薄膜を直接下地層とし、それを格段の保
護層、特により優れた耐擦傷性、耐摩耗性等を有する保
護層としようとするものには、到底採用できないもので
ある。
Furthermore, in the water repellent article and the method for producing the same described in, for example, Japanese Patent Laid-Open No. 5-310444, a silicon dioxide coating is used as an underlayer on the glass surface, and an organic silazane compound is added to the silazane water repellent. It is used as a base layer for the UV-absorbing thin film, and is used as a protective layer, especially for those with outstanding scratch resistance and abrasion resistance. It cannot be done.

【0032】[0032]

【問題点を解決するための手段】本発明は、従来のかか
る問題点に鑑みてなしたものであって、紫外/可視領域
境界をシャープにカットするようにしながら紫外線吸収
性能を高めるだけではなく、比較的高温の焼成でなる無
機質の紫外線吸収膜と低温硬化型のポリシラザン系混合
物溶液により被覆成膜した保護層を巧みに組み合わせる
ことで、クラック等の欠陥を防止でき、単板で外装用と
して使用可能な優れた耐薬品性、耐擦傷性ならびに耐久
性を有することはもちろん、種々の過酷な条件下、環境
下でもことに耐摩耗性や耐擦傷性ならびに耐久性を格段
に発揮して優れるものとなる有用な紫外線遮蔽ガラスを
容易にかつ効率よく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 conventional problems, and not only enhances the ultraviolet absorption performance while sharply cutting the ultraviolet / visible region boundary. By cleverly combining an inorganic ultraviolet absorbing film that is fired at a relatively high temperature and a protective layer that is formed by coating with a low-temperature-curable polysilazane-based mixture solution, defects such as cracks can be prevented, and a single plate can be used as an exterior product. Not only does it have excellent chemical resistance, scratch resistance, and durability that can be used, but it also exhibits outstanding wear resistance, scratch resistance, and durability, even under various severe conditions and environments. (EN) A useful and useful UV-shielding glass is provided easily and efficiently.

【0033】すなわち、本発明は、透明基材の表面に形
成した無機質でなる紫外線吸収膜の表面上に、ポリシラ
ザン系混合物の溶液を被覆成膜してなることを特徴とす
る紫外線遮蔽ガラス。
That is, the present invention is an ultraviolet shielding glass characterized in that a solution of a polysilazane-based mixture is coated on the surface of an inorganic ultraviolet absorbing film formed on the surface of a transparent substrate.

【0034】ならびに、前記無機質でなる紫外線吸収膜
が、酸化亜鉛膜または酸化亜鉛系膜であることを特徴と
する上述した紫外線遮蔽ガラス。また、前記無機質でな
る紫外線吸収膜が、酸化セリウムまたは酸化セリウム系
膜であることを特徴とする上述した紫外線遮蔽ガラス。
In addition, the above-mentioned ultraviolet ray shielding glass, wherein the inorganic ultraviolet ray absorbing film is a zinc oxide film or a zinc oxide based film. Further, the above-mentioned ultraviolet shielding glass, wherein the inorganic ultraviolet absorbing film is cerium oxide or a cerium oxide-based film.

【0035】さらに、前記ポリシラザン系混合物が、低
温硬化型ポリシラザン系混合物であることを特徴とする
上述した紫外線遮蔽ガラス。さらにまた、前記低温硬化
型ポリシラザン系混合物が、ポリ(ペルヒドロシラザ
ン)系を主体とするものであることを特徴とする上述し
た紫外線遮蔽ガラスをそれぞれ提供するものである。
Further, the above-mentioned ultraviolet-shielding glass, wherein the polysilazane-based mixture is a low temperature-curable polysilazane-based mixture. Furthermore, the above-mentioned UV-shielding glass is provided, characterized in that the low-temperature-curable polysilazane-based mixture is mainly composed of poly (perhydrosilazane).

【0036】ここで、前述したように、前記無機質でな
る紫外線吸収膜としたのは、無機質でなる紫外線吸収膜
がどちらかといえば硬い膜となり、ポリシラザン系混合
物、ことに低温硬化型ポリシラザン系混合物であっても
表面硬度が硬いものとなり、しかも従来得られないよう
な格段の耐擦傷性、耐摩耗性ならびに耐久性を達成し実
現できるとともに、下地層となる無機質の紫外線吸収膜
が比較的厚い膜とでき、ポリシラザン系混合物からなる
保護膜とが整合してクラック等の欠陥を発現することも
なく、紫外線吸収性能も充分高めたものとすることがで
きかつその性能を変化させることなく維持発揮できるか
らである。
Here, as described above, the ultraviolet absorbing film made of the inorganic material means that the ultraviolet absorbing film made of the inorganic material becomes a rather hard film, and the polysilazane-based mixture, especially the low temperature-curable polysilazane-based mixture is used. Even if it is, the surface hardness becomes harder, and it is possible to achieve remarkable scratch resistance, abrasion resistance and durability that could not be obtained conventionally, and at the same time, the inorganic ultraviolet absorbing film as the base layer is relatively thick It can be made into a film, it does not develop defects such as cracks by matching with the protective film made of a polysilazane-based mixture, and it is possible to have sufficiently enhanced ultraviolet absorption performance and maintain it without changing its performance Because you can.

【0037】また、前記酸化亜鉛膜または酸化亜鉛系膜
としては、例えば2-エチルヘキサン酸亜鉛、ナフテン酸
亜鉛等の金属石鹸系亜鉛、また例えばジエトキシ亜鉛、
ジプロポキシ亜鉛、ジプトキシ亜鉛等の亜鉛アルコキシ
ド系、また例えばジトリフルオロ酢酸亜鉛等のトリフル
オロ酢酸亜鉛塩系、さらに例えば酸化亜鉛微粒子含有シ
リカ等の酸化亜鉛微粒子含有系などが挙げられる。
Examples of the zinc oxide film or zinc oxide-based film include metal soap-based zinc such as zinc 2-ethylhexanoate and zinc naphthenate, and diethoxyzinc zinc, for example.
Examples thereof include zinc alkoxides such as dipropoxy zinc and diptoxy zinc, zinc trifluoroacetate salts such as zinc ditrifluoroacetate, and zinc oxide fine particles-containing systems such as silica containing zinc oxide fine particles.

【0038】また、酸化亜鉛系膜で酸化亜鉛と共存せし
めることができるものとしては、例えばSiO2、TiO2、Al
2O3 、CeO2、ZrO2、SnO2、In2O3 あるいはこれらの複合
物等が挙げられ、ことに吸収波長が紫外/可視領域境界
(例えば、400nm 付近)に効果があり、その添加量とし
ては0.1 〜6 wt%程度であって、0.1 wt%未満では効果
がなく、6 wt%を超えると溶解度の限界に近くなり、再
結晶を析出してくるようになって塗膜欠陥を生じ易くな
るし、必要以上の添加は不経済となり、好ましくは1乃
至3wt%程度である。
Further, examples of the zinc oxide type film which can coexist with zinc oxide include, for example, SiO 2 , TiO 2 and Al.
2 O 3 , CeO 2 , ZrO 2 , SnO 2 , In 2 O 3 or a compound of these, etc. are mentioned. Especially, the absorption wavelength has an effect on the ultraviolet / visible region boundary (for example, near 400 nm), and its addition The amount is about 0.1 to 6 wt%, and if it is less than 0.1 wt%, it has no effect, and if it exceeds 6 wt%, it approaches the solubility limit, and recrystallization precipitates to cause coating film defects. It is liable to occur, and addition of more than necessary becomes uneconomical, and it is preferably about 1 to 3 wt%.

【0039】さらに、前記酸化セリウムまたは酸化セリ
ウム系膜としては、例えばテトラ(1−メトキシ−エトキ
シ)セリウム、テトラブトキシセリウム等のセリウムア
ルコキシド系、また例えばUV−70(日板研究所製)等の
酸化セリウム微粒子含有系、さらに例えば(テトライソ
プロポシキチタン+硝酸セリウム)のアルコール溶液、
テトラブトキシチタン+テトラ(1−エトキシ−エトキ
シ)セリウムのアルコール溶液等の酸化チタン・酸化セ
リウム系などが挙げられる。
Further, the cerium oxide or cerium oxide-based film is, for example, a cerium alkoxide-based film such as tetra (1-methoxy-ethoxy) cerium or tetrabutoxycerium, or UV-70 (manufactured by Nippa Institute). A system containing fine particles of cerium oxide, for example, an alcohol solution of (tetraisopropoxy titanium + cerium nitrate),
Examples thereof include titanium oxide / cerium oxide-based compounds such as an alcohol solution of tetrabutoxytitanium + tetra (1-ethoxy-ethoxy) cerium.

【0040】さらにまた、前記紫外線吸収膜の溶液とし
ては、例えばプロパナール、ブタノールなどの希釈溶媒
などを利用して濃度、粘度あるいは膜厚の関係によって
調製すればよく、例えばその濃度としては約1〜20wt%
程度、好ましくは約5〜10wt%程度、粘度としては2〜
10cP程度、さらに膜厚としては0.01〜1.5 μ程度、好ま
しくは0.1 〜1.0 μ程度、より好ましくは0.2 〜0.5 μ
程度である。
Further, the solution of the ultraviolet absorbing film may be prepared by using a diluting solvent such as propanal, butanol or the like depending on the concentration, the viscosity or the film thickness. For example, the concentration is about 1 ~ 20wt%
Degree, preferably about 5 to 10 wt%, and the viscosity is 2 to
About 10 cP, and the film thickness is about 0.01 to 1.5 μ, preferably about 0.1 to 1.0 μ, more preferably 0.2 to 0.5 μ.
It is a degree.

【0041】なお、マイグレーション現象の発現防止あ
るいは密着性をより向上せしめるため、その他ギラギラ
の低減等に、下地層としてSiO2薄膜等を用いても良いこ
とは言うまでもない。
It is needless to say that a SiO 2 thin film or the like may be used as the underlayer in order to prevent the occurrence of the migration phenomenon or further improve the adhesiveness, and to reduce other glare.

【0042】さらにまた、上述したような前記紫外線吸
収膜用溶液の被膜法としては、均一膜厚となるように、
例えばディッピング法、スプレー法、フローコート法、
スピンコート法あるいは印刷法等さらに既存の被膜法で
塗布し被膜とし、例えば約150 ℃程度以上で約15分間前
後程度加熱乾燥するものであり、加熱不足であればシリ
カ系膜の密着性が悪化し、しかも表面硬度を充分高くす
ることができなくなり、また加熱が過多になるとソーダ
ライムガラス中に含まれるナトリウムイオンのマイグレ
ーション現象による紫外線吸収性能の低下、くもりある
いはクラック等を発現し易くなる。
Furthermore, as a method of coating the solution for the ultraviolet absorbing film as described above, a uniform film thickness is obtained.
For example, dipping method, spray method, flow coating method,
It is applied by a spin coating method, a printing method, or another existing coating method to form a coating. For example, it is dried by heating at about 150 ° C or higher for about 15 minutes, and if insufficient heating, the adhesion of the silica-based film deteriorates. Moreover, the surface hardness cannot be made sufficiently high, and if the heating is excessive, the ultraviolet absorption performance is deteriorated due to the migration phenomenon of sodium ions contained in the soda lime glass, and clouding or cracks easily occur.

【0043】さらに、塗布環境としては、例えば温度約
15〜25℃程度、湿度約40〜50RH%程度、さらにクリーン
度10,000以下程度が塗膜欠陥の防止の点で好ましい。コ
ーティング溶液の塗布性能を改善するため、フロー改良
剤あるいはレオロジーコントロール剤などを適宜添加し
てもよいことは言うまでもない。
Further, as the coating environment, for example, a temperature of about
About 15 to 25 ° C, a humidity of about 40 to 50 RH%, and a cleanliness of about 10,000 or less are preferable from the viewpoint of preventing coating film defects. It goes without saying that a flow improver, a rheology control agent or the like may be appropriately added in order to improve the coating performance of the coating solution.

【0044】さらにまた、ポリシラザン系混合物として
は、低温硬化型ポリシラザン系混合物が好ましく、具体
的には例えばポリ(ペルヒドロシラザン)系を主体とす
るもの〔例えば東燃社製〕であって、なかでも該固形分
濃度が5〜40wt%程度(残りが例えばキシレンおよび硬
化触媒等)であるものである。
Furthermore, as the polysilazane-based mixture, a low temperature-curable polysilazane-based mixture is preferable, and for example, a poly (perhydrosilazane) -based mixture (for example, manufactured by Tonensha Co., Ltd.) is particularly preferable. The solid content concentration is about 5 to 40 wt% (the rest is, for example, xylene and a curing catalyst).

【0045】また該混合物の被覆成膜については、均一
膜厚となるような、例えばディッピング法、スプレー
法、フローコート法、スピンコート法あるいは印刷法な
どが利用でき、膜厚としては約0.1 〜3μ程度であり、
約0.2 〜2.0 μ程度が好ましく、膜厚が0.1 μ程度未満
と薄いと例えば長期的な表面保護の効果が少なくなり、
また3μ程度を超えるように厚いと加熱乾燥硬化時にク
ラックを発現し易く、かつ経済的でなくなるものであ
る。さらに加熱乾燥硬化には約100 ℃程度以上約400 ℃
程度以下の温度で処理する必要があり、好ましくは約15
0 〜350 ℃程度であり、約10〜90分間程度、好ましくは
約30〜60分間前後程度の処理が表面硬度を高める上で好
ましい。なお塗布する際の環境としては、例えば温度が
約25℃程度の常温で相対湿度が約20〜50%RH程度、好ま
しくは約40%RH前後程度の空調された環境で行うことが
望ましい。
For forming a coating film of the mixture, for example, a dipping method, a spray method, a flow coating method, a spin coating method or a printing method can be used so as to obtain a uniform film thickness. About 3μ,
About 0.2 to 2.0 μ is preferable, and when the film thickness is less than 0.1 μ, for example, the long-term surface protection effect decreases,
On the other hand, if it is thicker than about 3 μm, cracks are likely to appear during heat-drying and curing, and it is not economical. Furthermore, about 100 ℃ or more, about 400 ℃ for heat drying and curing
It should be processed at a temperature below about 15 ° C, preferably about 15 ° C.
A treatment at about 0 to 350 ° C. for about 10 to 90 minutes, preferably about 30 to 60 minutes is preferable for increasing the surface hardness. It is desirable that the application environment is, for example, an air-conditioned environment in which the temperature is about 25 ° C. and the relative humidity is about 20 to 50% RH, preferably about 40% RH.

【0046】また、ポリシラザン系混合物の溶液におけ
る希釈溶媒については、芳香族化合物としては例えばベ
ンゼン、トルエン、キシレン、またエーテル化合物とし
ては例えばエチルエーテル、テトラヒドロフラン(THF)
、また塩素化合物としては例えば塩化メチレン、四塩
化炭素、さらにケトン化合物としては例えばブチルカル
ビトールアセテート等である。
Regarding the diluting solvent in the solution of the polysilazane-based mixture, aromatic compounds such as benzene, toluene and xylene, and ether compounds such as ethyl ether and tetrahydrofuran (THF) are used.
The chlorine compound is, for example, methylene chloride and carbon tetrachloride, and the ketone compound is, for example, butyl carbitol acetate.

【0047】さらにまた、前記透明基材としては、例え
ば所謂フロートガラス等の無機質のガラス基板であっ
て、無色有色を問わず、ことに形状等に特に限定される
ものではなく各種形状に、また大きさあるいは特異構成
のもの、例えば曲げ板ガラスとしてはもちろん、各種強
化ガラスや強度アップガラス、平板や単板で使用できる
とともに、複層ガラスあるいは合せガラスとしても適用
できることは言うまでもない。
Further, the transparent base material is, for example, an inorganic glass substrate such as so-called float glass, which may be colorless or colored and is not particularly limited in shape or the like, and may be in various shapes. It goes without saying that it can be used not only as a glass having a size or a peculiar structure, for example, a bent glass plate, but also as various tempered glass, a strengthened glass, a flat plate or a single plate, and can be applied as a multi-layer glass or a laminated glass.

【0048】[0048]

【作用】前述したとおり、本発明によれば、ガラス基板
表面に無機質の紫外線吸収膜を形成し、該紫外線吸収膜
上にポリシラザン系混合物の溶液で被覆した紫外線遮蔽
ガラスであるので、下地層としての紫外線吸収膜を比較
的高い温度、例えば約500 ℃程度で焼成する高温型で比
較的硬いしっかりした膜とでき、しかも比較的厚い紫外
線吸収膜、例えば約1.5 μ程度の厚膜にしたとしても、
被覆するポリシラザン系混合物の溶液が低温硬化処理、
例えば150 〜300 ℃程度での焼成成膜であるため、紫外
線吸収膜にクラックやガラス基板からのナトリウムイオ
ンのマイグレーション現象を発現するようなダメージを
与えることなく、紫外線吸収膜の紫外線吸収性能を高め
かつ維持発揮することができる。
As described above, according to the present invention, an inorganic ultraviolet absorbing film is formed on the surface of a glass substrate, and the ultraviolet absorbing glass is coated with a solution of a polysilazane-based mixture on the ultraviolet absorbing film. The UV absorbing film can be made into a relatively hard and firm film by baking at a relatively high temperature, for example, about 500 ° C. Even if a relatively thick UV absorbing film is made, for example, a thick film of about 1.5 μ. ,
The solution of the polysilazane-based mixture to be coated is a low temperature curing treatment,
For example, since the film is baked at about 150 to 300 ° C, the UV absorption performance of the UV absorption film can be improved without causing damage to the UV absorption film such as cracks or migration phenomenon of sodium ions from the glass substrate. And can maintain and exert.

【0049】さらにポリシラザン系混合物の溶液から得
た特異なシリカ系膜(例えば、SIMS等の表面分析で、該
膜の部分的なところ、例えば被覆接着部分においてNが
残存する等)を保護膜としたことで、400nm 付近におい
て紫外/可視領域の境界を透明で着色することなくシャ
ープにカットするようにしながら紫外線吸収膜の性能を
変化させることなく存分に発揮せしめることができ、こ
とに比較的厚い膜厚の上記特異なシリカ系膜でもクラッ
ク等の発現もなく低温硬化処理で紫外線吸収膜への密着
性が高くでき、アモルフアス状でも稠密なものとなり、
しかも例えば鉛筆硬度が9Hないしはそれ以上と硬く、膜
強度や平滑性も向上し、密着性や耐薬品性はもとより特
に耐摩耗性、耐擦傷性あるいは耐久性を格段に向上せし
め、ビルや住宅、車両あるいは各種の窓材等外装用とし
ての使用はもちろん充分可能であり、ことに自動車用窓
ガラスのフロントガラス、リアガラスおよび昇降用サイ
ドドアガラスなどのより過酷な使用条件と環境のなかで
も比較的に長期的な使用が可能となる等、有用な紫外線
遮蔽ガラスとなし得たものであって、低温硬化型処理で
ある簡単なコーティング処理によって容易にかつ高効率
で安価に得ることができ、提供するものである。
Further, a peculiar silica-based film obtained from the solution of the polysilazane-based mixture (for example, N is left at a partial portion of the film by surface analysis such as SIMS, for example, at a coating adhesion part) is used as a protective film. By doing so, it is possible to maximize the performance of the UV absorbing film without changing the performance while cutting the boundary between the UV / visible region around 400 nm sharply without coloring with transparency. Even with the peculiar silica-based film having a thick film thickness, there is no occurrence of cracks or the like, and the adhesion to the ultraviolet absorbing film can be increased by the low temperature curing treatment, and even the amorphous form becomes dense,
Moreover, for example, the pencil hardness is as hard as 9H or more, the film strength and smoothness are improved, and the adhesion and chemical resistance as well as the abrasion resistance, the scratch resistance and the durability are greatly improved, and the building, the house, Of course, it can be used as an exterior material for vehicles or various window materials, especially in the more severe operating conditions and environments such as windshields of automobile windows, rear glass and side door glass for lifting. It is a useful UV-shielding glass that can be used for a long period of time, and can be easily and efficiently obtained at low cost by a simple coating process that is a low-temperature curing process. To do.

【0050】[0050]

【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 the embodiment.

【0051】実施例1 大きさ約300mm x300mm 、厚さ約3mm のクリア・フロー
トガラス基板を中性洗剤、水すすぎ、アルコールで順次
洗浄し、乾燥した後、アセトンで払拭し被膜用ガラス基
板とした。
Example 1 A clear float glass substrate having a size of about 300 mm × 300 mm and a thickness of about 3 mm was sequentially washed with a neutral detergent, water rinse, alcohol, dried, and then wiped with acetone to form a glass substrate for coating. .

【0052】また、2-エチルヘキサン酸亜鉛(18%)10
0 g、脱水ひまし油脂肪酸(リノール酸含有量86%)80
g、レベリング剤としてTSF400〔東芝シリコーン(株)
製〕5gおよび希釈溶媒として混合キシレン315 gを混
合攪拌することで酸化亜鉛被膜用塗布溶液を調製した。
Also, zinc 2-ethylhexanoate (18%) 10
0 g, dehydrated castor oil fatty acid (linoleic acid content 86%) 80
g, TSF400 as a leveling agent [Toshiba Silicone Co., Ltd.
5 g and mixed xylene 315 g as a diluting solvent were mixed and stirred to prepare a zinc oxide coating solution.

【0053】次に、該被覆用ガラス基板の片面をフイル
ムマスキングし、上記した調製済の酸化亜鉛被膜用塗布
溶液に該被覆用ガラス基板を浸漬し、約20cm/min 程度
のスピードで引き上げて片面に塗膜を形成した。
Then, one surface of the glass substrate for coating is film-masked, the glass substrate for coating is dipped in the prepared coating solution for zinc oxide film described above, and pulled up at a speed of about 20 cm / min. A coating film was formed on.

【0054】次いで、約150 ℃程度で約15分間程度遠赤
外線炉で該塗膜を乾燥硬化し、さらに約500 ℃程度で約
15分間程度電気炉で焼成し成膜した。該成膜の膜厚約0.
93μ程度の均一透明な酸化亜鉛からなる紫外線吸収膜を
得た。
Then, the coating film is dried and hardened in a far infrared furnace at about 150 ° C. for about 15 minutes, and further at about 500 ° C.
The film was formed by firing in an electric furnace for about 15 minutes. The film thickness of the film formation is about 0.
An ultraviolet absorbing film of uniform transparent zinc oxide having a thickness of about 93 μm was obtained.

【0055】さらに次いで、ポリ(ペルヒドロシラザ
ン)を主体として硬化触媒等を添加し、希釈溶媒として
キシレンを用い、固形分濃度を約20wt%となるポリシラ
ザン系混合物溶液を調製した。〔東燃(株)製の東燃ポ
リシラザン等〕続いて、約25℃、約40%RHの空調された
クリーンルーム状態内で、上記酸化亜鉛からなる紫外線
吸収膜で被覆したガラス基板を上記した調製済のポリシ
ラザン系混合物溶液に浸漬し塗布後、該塗膜を約10分間
風乾し、さらに約300 ℃の熱風循環乾燥器に約30分間入
れ硬化し、シリカ系膜を得た。該膜は無色透明のクラッ
クのない良好なものであり、その膜厚は約0.3 μ程度で
あった。
Then, a curing catalyst or the like containing poly (perhydrosilazane) as a main component was added, and xylene was used as a diluting solvent to prepare a polysilazane-based mixture solution having a solid content concentration of about 20 wt%. [Tonen Corporation's Tonen Polysilazane, etc.] Then, in a clean room state of about 25 ° C. and about 40% RH in air conditioning, a glass substrate coated with the ultraviolet absorbing film made of the above zinc oxide was prepared as described above. After coating by dipping in a polysilazane-based mixture solution, the coating film was air-dried for about 10 minutes, and then placed in a hot-air circulating dryer at about 300 ° C. for about 30 minutes to be cured to obtain a silica-based film. The film was colorless and transparent and had no crack, and the film thickness was about 0.3 μm.

【0056】得られた紫外線吸収透明体である紫外線遮
蔽ガラスを下記した性能評価法に従って評価した。 (性能評価法) 紫外線吸収性:紫外/可視分光光度計で吸収スペクトル
パターンを測定。
The ultraviolet-shielding glass, which is the obtained ultraviolet-absorbing transparent body, was evaluated according to the performance evaluation method described below. (Performance Evaluation Method) Ultraviolet Absorption: Absorption spectrum pattern is measured with an ultraviolet / visible spectrophotometer.

【0057】紫外線(280 〜38nm)透過率はISO 9050の
規格に基づいて計算したもの。 耐摩耗性: JIS R 3221に準拠、摩耗輪CSー10F 、荷
重 500g、1000回転後の△H(ヘーズ)値(%)。
Ultraviolet (280-38 nm) transmittance is calculated based on the standard of ISO 9050. Abrasion resistance: Conforms to JIS R 3221, wear wheel CS-10F, load 500g, ΔH (haze) value (%) after 1000 rotations.

【0058】硬度: 鉛筆硬度。 密着性: JIS K5400 に準拠、碁盤目(1mm口)テ
ープ剥離残数を/100で表示。
Hardness: Pencil hardness. Adhesion: In accordance with JIS K5400, the cross-cut (1mm mouth) tape peeling remaining number is displayed as / 100.

【0059】 耐薬品性: 耐酸性---------3wt%希H2SO4 浸漬テストで24hr。 耐アルカリ性---3wt%NaOH水溶液 浸漬テストで24hr。 耐溶剤性-------100%塩化メチレン 浸漬テストで24hr。Chemical resistance: Acid resistance --------- 3wt% Dilute H 2 SO 4 immersion test for 24hrs. Alkali resistance --- 3wt% NaOH aqueous solution 24 hours in immersion test. Solvent resistance ------ 100% methylene chloride 24 hours in immersion test.

【0060】耐候性: JIS D0205 に準拠、サンシ
ャインカーボンウェザーメーターで目視異常(膜クラッ
ク、剥離、顕著な黄変)がみられるまでの時間。
Weather resistance: According to JIS D0205, the time until visual abnormality (film crack, peeling, noticeable yellowing) is observed with a sunshine carbon weather meter.

【0061】その結果、紫外線(波長280 〜380nm )で
は透過率5%以下で紫外線を遮蔽するものであって、充
分な透視性でシャープにカットでき、耐摩耗性もテーバ
ーテスト後のヘーズ値(△H)が約2.3 %と耐擦傷性も
優れ、耐候性も5000時間以上で目視および紫外線透過率
に異常がなく、耐薬品性も異常なく、優れた耐久性を有
する紫外線遮蔽ガラスであった。なお鉛筆硬度は9H以上
であった。
As a result, the ultraviolet ray (wavelength 280 to 380 nm) shields the ultraviolet ray with a transmittance of 5% or less, can be sharply cut with sufficient transparency, and the abrasion resistance has a haze value after the Taber test ( ΔH) was about 2.3%, which was excellent in scratch resistance, weather resistance was 5000 hours or more, and there was no abnormality in visual observation and ultraviolet transmittance, and there was no abnormality in chemical resistance, and it was an ultraviolet shielding glass having excellent durability. . The pencil hardness was 9H or higher.

【0062】自動車用窓ガラスのフロントガラスやリア
ガラスや昇降するサイドドアガラスにおいても比較的長
期間使用可能となるものであり、従来より格段の耐擦傷
性、耐摩耗性、耐久性を有するものであった。
It can be used for a relatively long period of time even on windshields and rear windows of window glass for automobiles, and side door glass that moves up and down, and has much more scratch resistance, abrasion resistance, and durability than ever before. there were.

【0063】実施例2 実施例1と同様なガラス基板に、実施例1と同様の酸化
亜鉛被膜用塗布溶液を用い、実施例1と同様にして被膜
しさらに乾燥、硬化、焼成をして成膜した。実施例1と
同様程度の膜厚が約0.8 μ程度の酸化亜鉛膜でなる紫外
線吸収膜を得た。
Example 2 A glass substrate similar to that in Example 1 was coated with the same zinc oxide coating solution as in Example 1 to form a coating film, which was then dried, cured, and baked. Filmed An ultraviolet absorbing film made of a zinc oxide film having a film thickness of about 0.8 μ, which is similar to that of Example 1, was obtained.

【0064】次いで、実施例1と同様のポリシラザン系
混合物溶液を該酸化亜鉛膜でなる紫外線吸収膜上に、実
施例1と同様の環境でスピンコートによって塗膜し、実
施例1と同様にして約250 ℃で約60分間で低温乾燥硬化
し、シリカ系膜を得た。該膜は無色透明のクラックのな
い良好なものであり、その膜厚は約1.1 μ程度であっ
た。
Then, a polysilazane-based mixture solution similar to that in Example 1 was applied onto the ultraviolet absorbing film made of the zinc oxide film by spin coating in the same environment as in Example 1, and then in the same manner as in Example 1. Low temperature dry curing was performed at about 250 ° C. for about 60 minutes to obtain a silica-based film. The film was colorless and good without cracks, and the film thickness was about 1.1 μm.

【0065】得られた紫外線吸収透明体である紫外線遮
蔽ガラスを実施例1と同様に評価した。紫外線透過率5.
2 %と前記紫外線を遮蔽するものであって、紫外線遮蔽
以外の特性、例えば耐薬品性、耐候性等はもちろん優
れ、前記ヘーズ値(△H)が約2.7 %、鉛筆硬度が9H以
上となる等、実施例1と同様に所期の優れた紫外線遮蔽
ガラスであった。
The obtained ultraviolet-shielding glass which is an ultraviolet-absorbing transparent body was evaluated in the same manner as in Example 1. UV transmittance 5.
2% and the above-mentioned ultraviolet rays are shielded. Of course, the characteristics other than the ultraviolet ray shielding, such as chemical resistance and weather resistance, are excellent, and the haze value (ΔH) is about 2.7% and the pencil hardness is 9H or more. As was the case with Example 1, it was an excellent ultraviolet-shielding glass.

【0066】なお、前記酸化亜鉛被膜用塗布溶液に例え
ば3〜25wt%程度のシリコーンオイルを添加したもので
も実施例1および2と同様の結果を得た。実施例3 実施例1と同様なガラス基板に、酸化亜鉛微粒子含有塗
料(住友大阪セメント社製)の溶液を用い、実施例1と
同様にして被膜し、乾燥硬化さらに約180 ℃で約15分間
程度焼成して成膜した。実施例1と同様程度の膜厚が約
1μ程度の酸化亜鉛膜でなる紫外線吸収膜を得た。
The same results as in Examples 1 and 2 were obtained even when the coating solution for the zinc oxide film was added with, for example, about 3 to 25 wt% of silicone oil. Example 3 A glass substrate similar to that used in Example 1 was coated with a solution of a zinc oxide fine particle-containing coating material (Sumitomo Osaka Cement Co., Ltd.) in the same manner as in Example 1, dried and cured, and further cured at about 180 ° C. for about 15 minutes. The film was fired to a degree to form a film. An ultraviolet absorbing film made of a zinc oxide film having a film thickness of about 1 μm, which is similar to that of Example 1, was obtained.

【0067】次いで、実施例1と同様のポリシラザン系
混合物溶液を該酸化亜鉛膜でなる紫外線吸収膜上に、室
温24℃で28%RHの空調されたクリーンルーム状態内で実
施例1と同様にして塗膜し、実施例1と同様に低温乾燥
硬化し、シリカ系膜を得た。該膜は無色透明のクラック
のない良好なものであり、その膜厚は約0.2 μ程度であ
った。
Then, the same polysilazane-based mixture solution as in Example 1 was placed on the ultraviolet absorbing film made of the zinc oxide film in the same manner as in Example 1 in an air-conditioned clean room state at room temperature 24 ° C. and 28% RH. A coating film was applied and dried at low temperature in the same manner as in Example 1 to obtain a silica film. The film was colorless and transparent and had no cracks, and the film thickness was about 0.2 μm.

【0068】得られた紫外線吸収透明体である紫外線遮
蔽ガラスを実施例1と同様に評価した。紫外線の遮蔽等
他の特性はもちろん、前記ヘーズ値(△H)が約1.7
%、鉛筆硬度が9H以上となる等、実施例1と同様に所期
の優れた紫外線遮蔽ガラスであった。
The ultraviolet-shielding glass, which is the obtained ultraviolet-absorbing transparent body, was evaluated in the same manner as in Example 1. The haze value (△ H) is about 1.7, as well as other characteristics such as UV shielding.
%, The pencil hardness was 9H or more, and the desired ultraviolet shielding glass was obtained as in Example 1.

【0069】実施例4 実施例1と同様なガラス基板に、ジブトキシ亜鉛25gを
53gのエタノールに溶解し、さらに安定化剤としてモノ
エタノールアミン10gを加えて調製した溶液を用い、実
施例1と同様にして被膜し、被膜後約2〜3分間空気中
で放置し加水分解を行い約150 ℃で約15分間程度乾燥硬
化し、さらに約400 ℃で約15分間程度焼成して成膜し
た。しかして膜厚が約0.3 μ程度の酸化亜鉛膜でなる紫
外線吸収膜を得た。
Example 4 25 g of dibutoxyzinc was added to the same glass substrate as in Example 1.
Using a solution prepared by dissolving in 53 g of ethanol and further adding 10 g of monoethanolamine as a stabilizer, coating was carried out in the same manner as in Example 1, and after the coating, hydrolysis was performed by leaving it in the air for about 2 to 3 minutes. The film was dried and hardened at about 150 ° C for about 15 minutes, and then baked at about 400 ° C for about 15 minutes to form a film. Thus, an ultraviolet absorbing film made of a zinc oxide film having a film thickness of about 0.3 μm was obtained.

【0070】次いで、実施例1と同様のポリシラザン系
混合物溶液を該酸化亜鉛膜でなる紫外線吸収膜上に、実
施例1と同様の環境の中でスピンコートによって塗膜
し、実施例1と同様に約270 ℃で約60分間程度の低温乾
燥硬化をし、シリカ系膜を得た。該膜は無色透明のクラ
ックのない良好なものであり、その膜厚は約1.4 μ程度
であった。
Then, a polysilazane-based mixture solution similar to that in Example 1 was applied onto the ultraviolet absorbing film made of the zinc oxide film by spin coating in the same environment as in Example 1, and the same as in Example 1. Then, low temperature dry curing was performed at about 270 ° C. for about 60 minutes to obtain a silica-based film. The film was colorless and transparent and had no cracks, and the film thickness was about 1.4 μ.

【0071】得られた紫外線吸収透明体である紫外線遮
蔽ガラスを実施例1と同様に評価した。波長400nm 以下
では透過率4.9 %と紫外線を遮蔽するものであって、紫
外線の遮蔽等他の特性はもちろん、前記ヘーズ値(△
H)が約2.2 %、鉛筆硬度が9H以上となる等、実施例1
と同様に所期の優れた紫外線遮蔽ガラスであった。
The ultraviolet-shielding glass, which is the obtained ultraviolet-absorbing transparent body, was evaluated in the same manner as in Example 1. At a wavelength of 400 nm or less, it has a transmittance of 4.9% and blocks UV rays. Of course, other characteristics such as UV blocking, as well as the haze value (△
H) is about 2.2% and the pencil hardness is 9H or more.
It was an excellent UV-shielding glass as expected.

【0072】実施例5 実施例1と同様なガラス基板に、トリフルオロ酢酸亜鉛
塩系の溶液(本庄ケミカル社製)を用い、実施例1と同
様にして被膜し、被膜後約2〜3分間空気中で放置し加
水分解を行い約150 ℃で約15分間程度乾燥硬化し、さら
に約400 ℃で約15分間程度焼成して成膜した。しかして
膜厚が約0.6 μ程度の酸化亜鉛膜でなる紫外線吸収膜を
得た。
Example 5 A glass substrate similar to that used in Example 1 was coated with a zinc trifluoroacetate solution (manufactured by Honjo Chemical Co., Ltd.) in the same manner as in Example 1, and about 2 to 3 minutes after the coating. It was left to stand in the air for hydrolysis, dried and hardened at about 150 ° C for about 15 minutes, and then baked at about 400 ° C for about 15 minutes to form a film. Thus, an ultraviolet absorbing film made of a zinc oxide film having a film thickness of about 0.6 μm was obtained.

【0073】次いで、実施例1と同様のポリシラザン系
混合物溶液を該酸化亜鉛膜でなる紫外線吸収膜上に、実
施例1と同様の環境の中でスピンコートによって塗膜
し、実施例1と同様に約280 ℃で約60分間程度の低温乾
燥硬化をし、シリカ系膜を得た。該膜は無色透明のクラ
ックのない良好なものであり、その膜厚は約1.1 μ程度
であった。
Then, a polysilazane-based mixture solution similar to that in Example 1 was applied onto the ultraviolet absorbing film made of the zinc oxide film by spin coating in the same environment as in Example 1, and the same as in Example 1. Then, it was dried and cured at a low temperature of about 280 ° C for about 60 minutes to obtain a silica film. The film was colorless and good without cracks, and the film thickness was about 1.1 μm.

【0074】得られた紫外線吸収透明体である紫外線遮
蔽ガラスを実施例1と同様に評価した。波長400nm 以下
では透過率8.1 %と紫外線を遮蔽するものであって、紫
外線の遮蔽等他の特性はもちろん、前記ヘーズ値(△
H)が約2.7 %、鉛筆硬度が9H以上となる等、実施例1
と同様に所期の優れた紫外線遮蔽ガラスであった。
The obtained ultraviolet-shielding glass which is an ultraviolet-absorbing transparent body was evaluated in the same manner as in Example 1. At a wavelength of 400 nm or less, it has a transmittance of 8.1% and blocks ultraviolet light. Of course, other characteristics such as ultraviolet light shielding, as well as the haze value (△
H) is about 2.7% and the pencil hardness is 9H or more.
It was an excellent UV-shielding glass as expected.

【0075】実施例6 実施例1と同様なガラス基板に、(株)日板研究所製の
UV-70 〔セリウム(CeO2)微粒子含有シリカ膜用:2液
混合タイプ〕の溶液を用い、実施例1と同様に浸漬し約
4mm/sec の引き上げスピードで被膜し、被膜後約200
℃で約10分間程度乾燥硬化して成膜した。しかして膜厚
が約0.6 μ程度のシリカを含む酸化セリウム系膜でなる
紫外線吸収膜を得た。なお該膜の屈折率は1.62程度であ
った。
Example 6 A glass substrate similar to that used in Example 1 was manufactured by Nippa Kenkyusho Co., Ltd.
Using a solution of UV-70 [for cerium (CeO 2 ) fine particle-containing silica film: two-liquid mixed type], dip it in the same manner as in Example 1 and form a film at a pulling speed of about 4 mm / sec.
A film was formed by drying and curing for about 10 minutes at ℃. Thus, an ultraviolet absorbing film made of a cerium oxide-based film containing silica having a thickness of about 0.6 μm was obtained. The refractive index of the film was about 1.62.

【0076】次いで、実施例1と同様のポリシラザン系
混合物溶液を該シリカを含む酸化セリウム系膜でなる紫
外線吸収膜上に、実施例1と同様の環境の中でディップ
法によって塗膜し、実施例1と同様に約250 ℃で約60分
間程度の低温乾燥硬化をし、シリカ系膜を得た。該膜は
無色透明のクラックのない良好なものであり、その膜厚
は約1.8 μ程度であった。
Then, a polysilazane-based mixture solution similar to that in Example 1 was applied on the ultraviolet absorbing film made of a cerium oxide-based film containing the silica by a dip method in the same environment as in Example 1 to carry out. In the same manner as in Example 1, low temperature dry curing was performed at about 250 ° C. for about 60 minutes to obtain a silica-based film. The film was colorless and transparent and had no crack, and the film thickness was about 1.8 μm.

【0077】得られた紫外線吸収透明体である紫外線遮
蔽ガラスを実施例1と同様に評価した。波長400nm 以下
では透過率15.2%と紫外線を遮蔽するものであって、紫
外線の遮蔽等他の特性はもちろん、前記ヘーズ値(△
H)が約2.5 %、鉛筆硬度が9H以上となる等、実施例1
と同様に所期の優れた紫外線遮蔽ガラスであった。
The obtained ultraviolet-shielding glass, which is an ultraviolet-absorbing transparent body, was evaluated in the same manner as in Example 1. It has a transmittance of 15.2% at a wavelength of 400 nm or less and shields ultraviolet rays. Not to mention other characteristics such as ultraviolet ray shielding, the haze value (△
H) is about 2.5% and the pencil hardness is 9H or more.
It was an excellent UV-shielding glass as expected.

【0078】実施例7 実施例1と同様なガラス基板に、濃度1mol /l のテト
ラ(1−エトキシ−エトキシ)セリウムと溶媒としてトル
エンの混合溶液を用い、実施例1と同様に浸漬し約4mm
/sec の引き上げスピードで被膜し、被膜後約200 ℃で
約10分間程度乾燥硬化して成膜した。しかして膜厚が約
0.25 μ程度の酸化セリウム系膜でなる紫外線吸収膜を
得た。なお、該膜の屈折率は2.12程度であった。
Example 7 A glass substrate similar to that in Example 1 was immersed in a mixed solution of tetra (1-ethoxy-ethoxy) cerium having a concentration of 1 mol / l and toluene as a solvent, and immersed in the same manner as in Example 1 to about 4 mm.
A film was formed at a pulling speed of / sec, and after the film was formed, the film was dried and cured at about 200 ° C. for about 10 minutes. The film thickness is about
An ultraviolet absorbing film made of a cerium oxide film having a thickness of about 0.25 μm was obtained. The refractive index of the film was about 2.12.

【0079】次いで、実施例1と同様のポリシラザン系
混合物溶液を該シリカを含む酸化セリア系膜でなる紫外
線吸収膜上に、実施例1と同様の環境の中でディップ法
によって塗膜し、実施例1と同様に約300 ℃で約30分間
程度の低温乾燥硬化をし、シリカ系膜を得た。該膜は無
色透明のクラックのない良好なものであり、その膜厚は
約0.4 μ程度であった。
Then, a polysilazane-based mixture solution similar to that of Example 1 was applied onto the ultraviolet absorbing film made of the ceria oxide-based film containing the silica by the dip method in the same environment as in Example 1 to carry out. In the same manner as in Example 1, low temperature dry curing was performed at about 300 ° C. for about 30 minutes to obtain a silica-based film. The film was colorless and transparent and had no crack, and the film thickness was about 0.4 μm.

【0080】得られた紫外線吸収透明体である紫外線遮
蔽ガラスを実施例1と同様に評価した。波長400nm 以下
では透過率12.2%と紫外線を遮蔽するものであって、紫
外線の遮蔽等他の特性はもちろん、前記ヘーズ値(△
H)が約2.8 %、鉛筆硬度が9H以上となる等、実施例1
と同様に所期の優れた紫外線遮蔽ガラスであった。
The obtained ultraviolet-shielding glass, which is an ultraviolet-absorbing transparent body, was evaluated in the same manner as in Example 1. It has a transmittance of 12.2% at a wavelength of 400 nm or less, and it blocks ultraviolet light. Not only other characteristics such as ultraviolet light blocking, but also the haze value (△
H) is about 2.8% and the pencil hardness is 9H or more.
It was an excellent UV-shielding glass as expected.

【0081】比較例1 実施例1と同様のガラス基板に、実施例1と同様の紫外
線吸収膜のみを成膜し、保護膜を施さないものとした。
Comparative Example 1 On a glass substrate similar to that of Example 1, only the ultraviolet absorbing film similar to that of Example 1 was formed and no protective film was applied.

【0082】得られた該紫外線吸収性ガラス基板につい
ては、例えば耐摩耗性のテーバーテストで約100 回転程
度で膜剥離が発現し、到底所期の紫外線遮蔽ガラスとは
言い難いものであった。
With respect to the obtained ultraviolet absorbing glass substrate, for example, in the abrasion-resistant Taber test, film peeling occurred after about 100 rotations, and it was hard to say that it was an expected ultraviolet shielding glass.

【0083】比較例2 実施例1と同様のガラス基板に、実施例2と同様の紫外
線吸収膜のみを成膜し、保護膜を施さないものとした。
Comparative Example 2 On a glass substrate similar to that of Example 1, only the ultraviolet absorbing film similar to that of Example 2 was formed, and no protective film was applied.

【0084】得られた該紫外線吸収性ガラス基板につい
ては、例えば耐摩耗性のテーバーテスト後のヘーズ値
(△H)が約5.5 %と耐擦傷性や耐摩耗性等があるもの
の、耐薬品性、耐候性が必ずしも充分でなく、到底所期
の紫外線遮蔽ガラスとは言い難いものであった。
Regarding the obtained ultraviolet absorbing glass substrate, for example, the haze value (ΔH) after the abrasion resistance Taber test is about 5.5%, and although it has scratch resistance and abrasion resistance, it has chemical resistance. However, the weather resistance was not always sufficient, and it was hard to say that it was an expected ultraviolet shielding glass.

【0085】比較例3 実施例1と同様のガラス基板に、市販の有機質の紫外線
吸収膜を成膜し、保護膜として実施例1と同様にし、約
200 ℃で約30分間の低温乾燥硬化し、膜厚約3.2 μのシ
リカ系膜を形成した。
Comparative Example 3 A commercially available organic ultraviolet absorbing film was formed on the same glass substrate as in Example 1, and the same protective film as in Example 1 was used.
It was dried and cured at 200 ° C. for about 30 minutes at low temperature to form a silica-based film having a thickness of about 3.2 μ.

【0086】得られた該紫外線吸収性ガラス基板につい
ては、例えば耐摩耗性のテーバーテスト後のヘーズ値
(△H)が約35.5%と耐擦傷性や耐摩耗性等が劣り、到
底所期の紫外線遮蔽ガラスとは言い難いものであった。
Regarding the obtained ultraviolet absorbing glass substrate, for example, the haze value (ΔH) after the abrasion resistance Taber test was about 35.5%, and the abrasion resistance and abrasion resistance were inferior. It was hard to say that it was UV shielding glass.

【0087】[0087]

【発明の効果】以上前述したように、本発明によれば、
光学特性を損なうことなく、無着色でかつ透明でしかも
紫外線を高い遮蔽、ことに400nm 付近において紫外/可
視領域の境界をシャープに紫外線を遮蔽することがで
き、密着性や耐薬品性に優れるものであることはもちろ
ん、さらに格段の耐擦傷性、耐摩耗性ならびに耐候性、
耐久性を備えるものとなし得ることができ、ビルあるい
は住宅、車両等の窓材など外装用としても単板で使用可
能なことはもちろん、ことに自動車用窓ガラスのフロン
トガラス、リアガラスあるいは昇降するサイドドアガラ
ス等の過酷な使用条件や環境においても、比較的長期的
に使用できることとなる等、種々の分野に広く採用でき
る有用な紫外線遮蔽ガラスを容易にかつ効率よく安価に
提供できるものである。
As described above, according to the present invention,
It is non-colored and transparent without damaging its optical characteristics, and also has a high UV shielding property. In particular, it can shield UV rays sharply at the boundary between the UV and visible regions around 400 nm, and has excellent adhesion and chemical resistance. Of course, it is also much more scratch resistant, abrasion resistant and weather resistant,
It can be made durable, and can be used as a single plate for exteriors such as window materials for buildings, houses, vehicles, etc., of course, windshields of automobile window glass, rear glass or elevating It is possible to provide a useful ultraviolet-shielding glass that can be widely adopted in various fields easily and efficiently at low cost, such that it can be used for a relatively long period of time even under severe use conditions and environments such as side door glass. .

Claims (5)

【特許請求の範囲】[Claims] 【請求項1】 透明基材の表面に形成した無機質でなる
紫外線吸収膜の表面上に、ポリシラザン系混合物の溶液
を被覆成膜してなることを特徴とする紫外線遮蔽ガラ
ス。
1. An ultraviolet-shielding glass, characterized in that a solution of a polysilazane-based mixture is coated on the surface of an inorganic ultraviolet-absorbing film formed on the surface of a transparent substrate.
【請求項2】 前記無機質でなる紫外線吸収膜が、酸化
亜鉛膜または酸化亜鉛系膜であることを特徴とする請求
項1記載の紫外線遮蔽ガラス。
2. The ultraviolet shielding glass according to claim 1, wherein the ultraviolet absorbing film made of an inorganic material is a zinc oxide film or a zinc oxide based film.
【請求項3】 前記無機質でなる紫外線吸収膜が、酸化
セリウムまたは酸化セリウム系膜であることを特徴とす
る請求項1記載の紫外線遮蔽ガラス。
3. The ultraviolet shielding glass according to claim 1, wherein the ultraviolet absorbing film made of an inorganic material is cerium oxide or a cerium oxide-based film.
【請求項4】 前記ポリシラザン系混合物が、低温硬化
型ポリシラザン系混合物であることを特徴とする請求項
1乃至3記載の紫外線遮蔽ガラス。
4. The ultraviolet light shielding glass according to claim 1, wherein the polysilazane-based mixture is a low temperature curable polysilazane-based mixture.
【請求項5】 前記低温硬化型ポリシラザン系混合物
が、ポリ(ペルヒドロシラザン)系を主体とするもので
あることを特徴とする請求項4記載の紫外線遮蔽ガラ
ス。
5. The ultraviolet light shielding glass according to claim 4, wherein the low temperature-curable polysilazane-based mixture is mainly composed of poly (perhydrosilazane) -based mixture.
JP28826894A 1994-11-22 1994-11-22 Uv shielding glass Pending JPH08143331A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP28826894A JPH08143331A (en) 1994-11-22 1994-11-22 Uv shielding glass

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP28826894A JPH08143331A (en) 1994-11-22 1994-11-22 Uv shielding glass

Publications (1)

Publication Number Publication Date
JPH08143331A true JPH08143331A (en) 1996-06-04

Family

ID=17727988

Family Applications (1)

Application Number Title Priority Date Filing Date
JP28826894A Pending JPH08143331A (en) 1994-11-22 1994-11-22 Uv shielding glass

Country Status (1)

Country Link
JP (1) JPH08143331A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8409663B2 (en) * 2007-04-27 2013-04-02 Guardian Industries Corp. Method of making a coated glass substrate with heat treatable ultraviolet blocking characteristics
JP2013119511A (en) * 2011-12-08 2013-06-17 Panasonic Corp Coated member
JP2017066381A (en) * 2015-09-30 2017-04-06 Hoya Candeo Optronics株式会社 Ultraviolet absorption coating, ultraviolet absorption film, light absorption film, optical element, optical unit and light irradiation device
CN111423130A (en) * 2020-03-31 2020-07-17 华南理工大学 Ultraviolet-cured hydrophobic transparent coating and preparation method and application thereof
CN114230194A (en) * 2021-12-08 2022-03-25 中稀产业发展(天津)集团有限公司 Rare earth-based ultraviolet shielding type coated glass

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8409663B2 (en) * 2007-04-27 2013-04-02 Guardian Industries Corp. Method of making a coated glass substrate with heat treatable ultraviolet blocking characteristics
JP2013119511A (en) * 2011-12-08 2013-06-17 Panasonic Corp Coated member
JP2017066381A (en) * 2015-09-30 2017-04-06 Hoya Candeo Optronics株式会社 Ultraviolet absorption coating, ultraviolet absorption film, light absorption film, optical element, optical unit and light irradiation device
CN111423130A (en) * 2020-03-31 2020-07-17 华南理工大学 Ultraviolet-cured hydrophobic transparent coating and preparation method and application thereof
CN114230194A (en) * 2021-12-08 2022-03-25 中稀产业发展(天津)集团有限公司 Rare earth-based ultraviolet shielding type coated glass

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