JPH10297938A - Privacy glass and its production - Google Patents
Privacy glass and its productionInfo
- Publication number
- JPH10297938A JPH10297938A JP9112072A JP11207297A JPH10297938A JP H10297938 A JPH10297938 A JP H10297938A JP 9112072 A JP9112072 A JP 9112072A JP 11207297 A JP11207297 A JP 11207297A JP H10297938 A JPH10297938 A JP H10297938A
- Authority
- JP
- Japan
- Prior art keywords
- film
- silica
- glass substrate
- glass
- sol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
-
- 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
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/44—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the composition of the continuous phase
- C03C2217/45—Inorganic continuous phases
-
- 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
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
- C03C2217/48—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase having a specific function
- C03C2217/485—Pigments
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ガラス基板にいわ
ゆるゾル−ゲル法により所望の膜を成膜してなり、適度
に遮光し、防眩する窓ガラスとして各種分野で採用でき
るプライバシ−ガラス、及びその製法に関するもので、
該プライバシ−ガラスは、特に建築用、自動車等の車両
用、船舶航空機等の輸送機用窓ガラスとして、単板ある
いは他のガラス板との合せ、複層ガラスとして好適に採
用できるものである。BACKGROUND OF THE INVENTION The present invention relates to a privacy glass which can be used in various fields as a window glass which is formed by forming a desired film on a glass substrate by a so-called sol-gel method, and which can appropriately shield light and prevent glare. And its manufacturing method,
The privacy glass can be suitably used as a window glass for a building, a vehicle such as an automobile, a transport machine such as a marine aircraft, or a combination of a single plate or another glass plate, and a double glazing.
【０００２】[0002]
【従来技術とその解決すべき課題】建築用ガラスや車両
用ガラス等の窓ガラスには、快適さ、断熱性、プライバ
シ−性等を得ることを目的として種々の着色ガラス、遮
光膜付きガラスや断熱膜付きガラスが提唱され、使用さ
れてきた。2. Description of the Related Art Various types of colored glass, glass with a light-shielding film, and the like for the purpose of obtaining comfort, heat insulation, privacy and the like are used for window glass such as architectural glass and vehicle glass. Glass with insulating films has been proposed and used.
【０００３】例えば、特公昭54-40568号公報には高反射
率高耐久性を有する熱線反射ガラスに関し、鉄酸化物、
クロム酸化物、およびコバルト酸化物を含む金属酸化物
被膜をガラス表面に形成した熱線反射ガラスであって、
可視光線反射率が35％以上ものが開示され、また、特開
平6-80441 号公報には、熱処理可能なスパッタ被膜され
たガラス製品およびその形成方法に関し、a)Ni（Ni合
金）の酸化物または窒化物からなる第１層と、b)Ni（Ni
合金）金属からなる第２層と、c)前記a)に記載の金属酸
化物または窒化物からなる第３層と、更にd)Sn, Zn, Ti
（それらの合金）の酸化物からなる第４層とを含むコ−
ティングを有するガラス基板からなる熱処理可能なガラ
ス製品であって、例えば膜面側の可視光線反射率が31〜
33％であることが開示されている。For example, Japanese Patent Publication No. 54-40568 discloses a heat ray reflective glass having a high reflectance and a high durability.
Chromium oxide, and a heat reflecting glass having a metal oxide film containing a cobalt oxide formed on the glass surface,
Japanese Unexamined Patent Publication No. 6-80441 discloses a sputter-coated glass product which can be heat-treated and a method for forming the glass product. Or a first layer of nitride and b) Ni (Ni
Alloy) a second layer of metal; c) a third layer of metal oxide or nitride as described in a) above; and d) Sn, Zn, Ti
And a fourth layer made of an oxide of these (alloys).
Heat-treatable glass product consisting of a glass substrate having a coating, for example, the visible light reflectance on the film surface side is 31 ~
It is disclosed to be 33%.
【０００４】これら公知の２例は金属化合物の熱分解
法、あるいはスパッタリング法により膜形成するもの
で、本発明におけるようなシリカ系のゾルをベースとす
るものではない。またガラス製品は反射が強く、ギラツ
キ感、すなわちグレアーな感を呈し、目に対する刺激が
強く、周辺環境、特に自然環境に順応し得るものではな
い。[0004] In these two known examples, a film is formed by a thermal decomposition method or a sputtering method of a metal compound, and is not based on a silica sol as in the present invention. Further, the glass product has a strong reflection, a glaring feeling, that is, a glare feeling, a strong stimulus to the eyes, and cannot adapt to the surrounding environment, especially the natural environment.
【０００５】また、特開平4-219347号公報には、薄膜付
窓ガラスの製造方法とその薄膜付窓ガラスに関し、ガラ
ス基板上に、光によりゲル化する塗布液をフレキソ印刷
により塗布した後、光照射し、さらに熱処理して薄膜を
形成することが、また塗布液としてキレート化剤と、そ
の存在下で光によりゲル化する金属アルコキシドと、更
に着色剤を含むことが開示され、あるいは更に予め着色
セラミックカラーインクにより印刷したうえで、前記塗
布液を塗布し、上記した如くの処理により薄膜を形成す
ることが開示されている。Japanese Patent Application Laid-Open No. 4-219347 discloses a method of manufacturing a window glass with a thin film and a window glass with the thin film, which comprises applying a coating solution which gels by light onto a glass substrate by flexographic printing. It is disclosed that a thin film is formed by irradiating light and further heat-treating, and that a chelating agent, a metal alkoxide that gels by light in the presence of the coating solution, and a colorant are further contained as a coating solution, It is disclosed that after printing with a colored ceramic color ink, the coating liquid is applied and a thin film is formed by the above-described processing.
【０００６】該公知例は、薄膜用原料としてキレート化
剤を含み、また光照射手段を採用するものであり、また
膜厚 200nm以下とするものであって本発明とは相違す
る。本発明における濃色グレー系プライバシーガラスを
得ようとすれば、複数回重ね塗りしたうえで上記成膜工
程を採るか、あるいは前記着色セラミックカラーインク
により印刷し、更に前記塗布液を塗布したうえで、上記
成膜工程を採らねばならず、製法手段が煩雑となる。The known example contains a chelating agent as a raw material for a thin film, employs light irradiation means, and has a film thickness of 200 nm or less, which is different from the present invention. If it is intended to obtain a dark gray privacy glass in the present invention, the above-mentioned film-forming step is performed after multiple coatings, or printing with the colored ceramic color ink, and further applying the coating liquid In addition, it is necessary to adopt the above-mentioned film forming process, and the manufacturing method becomes complicated.
【０００７】更に特開平8-73240 号公報には、ガラス着
色用発色剤に関し、AuやAg等の金属の超微粒子と、金属
の超微粒子を固定する有機金属化合物からなる固定剤
と、バインダ−樹脂と、M'（M'＝Si，B, Pから選択）で
表される元素を含む有機化合物であるガラス骨格成分
と、有機溶剤とからなる発色剤が開示されている。Further, Japanese Patent Application Laid-Open No. 8-73240 discloses a coloring agent for coloring a glass, which includes ultrafine particles of a metal such as Au or Ag, a fixing agent comprising an organic metal compound for fixing the ultrafine particles of a metal, and a binder. A color former comprising a resin, a glass skeleton component that is an organic compound containing an element represented by M ′ (M ′ = selected from Si, B, and P), and an organic solvent is disclosed.
【０００８】該公知例は、着色膜用原料としてバインダ
ー樹脂を用い、着色剤として金属を用いることにおいて
本発明と相違する。該公知例においては、ガラス着色用
発色剤として金属の超微粒子を用いているが、金属の吸
収波長域は複合型金属酸化物のそれに比べて狭く、従っ
て可視光全域での均一な吸収を得ることは困難で、無彩
色のグレ−色が得られ難い。The known example differs from the present invention in that a binder resin is used as a raw material for a colored film and a metal is used as a colorant. In this known example, ultrafine particles of a metal are used as a coloring agent for coloring a glass, but the absorption wavelength range of the metal is narrower than that of the composite metal oxide, and therefore, uniform absorption in the entire visible light range is obtained. It is difficult to obtain an achromatic gray color.
【０００９】或いは更に特開平8-208274号公報には、着
色膜形成用塗布液、着色膜及び着色膜を形成したガラス
物品に関し、Ti、V 、Cr、Mn、Fe、Co、Ni、Cu及びZnの
うち１種以上の元素を含む複合酸化物顔料を分散させた
液を含む着色膜形成用塗布液が、また該塗布液中にSn、
In、Zn、Al、Ti、Si及びGaの群から選ばれる１種以上の
金属化合物を含むことが、更に着色膜上に該着色膜より
低屈折率の被膜が順次形成されていることが開示されて
いる。Further, Japanese Patent Application Laid-Open No. 8-208274 discloses a coating liquid for forming a colored film, a colored film, and a glass article having the colored film formed thereon, which include Ti, V, Cr, Mn, Fe, Co, Ni, Cu and A coating liquid for forming a colored film including a liquid in which a composite oxide pigment containing one or more elements of Zn is dispersed, and Sn,
Including that at least one metal compound selected from the group consisting of In, Zn, Al, Ti, Si and Ga is disclosed, and that a film having a lower refractive index than the colored film is sequentially formed on the colored film. Have been.
【００１０】該公知例は、TV管パネルなど陰極線管用パ
ネル表面に適用されるものであり、ガラス本体の透過率
の低下を抑えつつ画面のコントラスト比を向上させるこ
とを狙いとするものであって、濃色グレー系プライバシ
ーガラスを得るものとは相違する。This known example is applied to the surface of a cathode ray tube panel such as a TV tube panel, and aims at improving the contrast ratio of the screen while suppressing the decrease in the transmittance of the glass body. This is different from that of obtaining a dark gray privacy glass.
【００１１】また、自動車用窓ガラスなどのような曲げ
強化における、より高温での処理、急冷強化処理におい
てはクラックなどの欠陥が発生し易いという危惧があ
る。本発明は、それら公知例とは異なり、耐擦傷性、耐
磨耗性、および耐薬品性に優れ、無彩色のグレー色調を
有し、プライバシー性に優れ、また光反射性を抑えてグ
レアー感がなく、目に対する刺激も小さく、周辺環境と
も調和し易いプライバシーガラスを提供するものであ
る。In addition, there is a concern that defects such as cracks are liable to occur in the treatment at a higher temperature or in the quenching and strengthening treatment in bending strengthening such as window glass for automobiles. The present invention is different from these known examples in that it has excellent scratch resistance, abrasion resistance, and chemical resistance, has an achromatic gray color tone, is excellent in privacy, and has reduced glare by suppressing light reflection. It is intended to provide a privacy glass that has no stimulus to the eyes, has little irritation to the eyes, and is easily harmonized with the surrounding environment.
【００１２】[0012]
【課題を解決するための手段】本発明は、プライバシー
ガラスに関し、 １）透明ガラス基板の表面に、２種以上の着色性の酸化
物成分からなる黒色系顔料を分散したシリカ系(A) のゾ
ルを前躯体とする濃色グレ−系の着色膜を形成してなる
プライバシ−ガラスであって、その可視光線透過率が20
〜40％、可視光線反射率が10％未満であること。Means for Solving the Problems The present invention relates to a privacy glass. 1) A silica (A) in which a black pigment composed of two or more coloring oxide components is dispersed on the surface of a transparent glass substrate. It is a privacy glass formed with a dark gray colored film having a sol as a precursor, and has a visible light transmittance of 20%.
~ 40%, the visible light reflectance is less than 10%.
【００１３】２）前記シリカ系(A) のゾルが、シリカ、
またはシリカとMeOx（Me＝Al, Ca,Mg, B の１種以上）
の混合ゾルからなり、シリカ：MeOxの重量比が80：20〜
100：０であること。2) The silica-based (A) sol is silica,
Or silica and MeOx (Me = at least one of Al, Ca, Mg, B)
And a weight ratio of silica: MeOx of 80: 20-
100: 0.
【００１４】３）前記１）および２）において、シリカ
系(A) の酸化物：黒色系顔料の酸化物重量比が40：60〜
60：40であること。3) In the above 1) and 2), the weight ratio of the oxide of the silica (A) to the oxide of the black pigment is from 40:60 to 40:60.
60:40.
【００１５】４）更に前記１）の透明ガラス基板に施し
た濃色グレー系の着色膜の上に、シリカ系(B) のゾルを
前躯体とする保護膜を形成してなること。4) Further, a protective film having a silica (B) sol as a precursor is formed on the dark gray colored film applied to the transparent glass substrate of 1).
【００１６】５）前記シリカ系(B) のゾルが、シリカと
MO2 （M ＝Ti, Zr, Ceの１種以上）の混合ゾルからな
り、シリカ：MO2 の重量比が70：30〜95：５であるこ
と、から構成される。5) The silica-based (B) sol comprises silica and
MO 2 becomes a mixed sol (M = Ti, Zr, 1 or more Ce), silica weight ratio of MO 2 is 70: 30 to 95: it is a 5, composed.
【００１７】さらに前記１）記載のプライバシ−ガラス
の製法に関し、 ６）(a) 透明ガラス基板を用意する工程と、(b) 黒色系
顔料：シリカ系(A) のゾルの酸化物重量比が40〜60：60
〜40となるべく調合した、黒色系顔料と、シリカ系(A)
のゾル用出発原料とを、分散剤と溶媒とを含む液に添加
し、撹拌混合して塗布液を調製する工程と、(c) 前記塗
布液を、前記ガラス基板表面上に塗布し、加熱乾燥して
膜を付着する工程と、(d）更に熱処理して成膜する工程
と、によってガラス基板面上に着色膜を形成すること。Further, with respect to the method for producing privacy glass described in 1) above, 6) (a) a step of preparing a transparent glass substrate, and (b) the oxide weight ratio of black pigment: silica (A) sol 40-60: 60
Black pigment and silica (A) prepared as much as possible
Adding a starting material for sol to a liquid containing a dispersant and a solvent, stirring and mixing to prepare a coating liquid, and (c) coating the coating liquid on the surface of the glass substrate, and heating. Forming a colored film on the surface of the glass substrate by a step of drying and attaching a film, and (d) a step of forming a film by further heat treatment.
【００１８】７）前記６）（a)〜(c) の方法により、ガ
ラス基板上に施した着色膜用塗布液を加熱乾燥後、引き
続き保護膜を形成するにあたり、(e) シリカ系(B) のゾ
ルにおけるシリカ：MO2 の重量比が70：30〜95：５とな
るべくシリカ系(B) のゾル用出発を、分散剤と溶媒とを
含む液に添加し、撹拌混合して塗布液を調製する工程
と、(f) 前記塗布液を前記ガラス基板表面上に塗布し、
加熱乾燥して膜を付着する工程と、(g) 更に熱処理して
成膜する工程と、によって着色膜面上に保護膜を形成す
ること、から構成される。7) According to 6) (a) to (c) above, after heating and drying the coating solution for the colored film applied on the glass substrate, (e) silica-based (B) ), A silica-based (B) sol starting solution is added to a solution containing a dispersant and a solvent so that the weight ratio of silica: MO 2 in the sol is 70:30 to 95: 5, and the mixture is stirred and mixed. Preparing a, and (f) applying the coating solution on the glass substrate surface,
Forming a protective film on the surface of the colored film by the steps of heating and drying to attach the film, and (g) forming a film by further heat treatment.
【００１９】なお、可視光線反射率は、特にことわりが
ない限り膜面側の反射率をいう。The visible light reflectance means the reflectance on the film surface side unless otherwise specified.
【００２０】[0020]
【発明の実施の形態】本発明において、透明ガラス基板
としては、アルカリ（ソーダ）石灰系ガラス、アルミノ
珪酸系ガラス、ほう珪酸系ガラス等各種のガラスが採用
でき、それら製板法はフロート法、フルコール法、ペン
バーノン法、ロールアウト法、ロールアウト−表面研磨
法等いずれでもよいが、ソーダ石灰系ガラスをフロート
法により製板したものが最も一般的である。DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, various glasses such as alkali (soda) lime glass, aluminosilicate glass, borosilicate glass and the like can be used as a transparent glass substrate. Any of the full coal method, the Pembernon method, the rollout method, the rollout-surface polishing method, etc. may be used, but the most common one is a soda-lime glass made by a float method.
【００２１】前記透明ガラス基板は、透明であれば着
色、無着色を問わないが、成膜後に所望のグレー系色調
を得ようとするなら、無色透明なガラスを採用するのが
よい。勿論金属線入りガラス等の介在物を有するガラス
や、強化板ガラス、曲げ板ガラス等の加工されたガラス
も対象となる。なお、平板状ガラス基板に本発明におけ
る濃色グレー系着色膜、あるいは更に保護膜を付着後、
熱曲げ処理および／または熱強化処理することにより、
膜形成（完成）を同時に行うことができる。The transparent glass substrate may be colored or uncolored as long as it is transparent, but if it is desired to obtain a desired gray color tone after film formation, it is preferable to use a colorless and transparent glass. Of course, a glass having inclusions such as a glass containing a metal wire, and a processed glass such as a reinforced plate glass and a bent plate glass are also applicable. Incidentally, after attaching the dark gray colored film of the present invention or a further protective film to the flat glass substrate,
By performing a heat bending process and / or a heat strengthening process,
Film formation (completion) can be performed simultaneously.
【００２２】本発明において、濃色グレー系着色膜を形
成するうえで、シリカ系(A) のゾル用の出発原料として
はシリコンアルコキシド（一部のアルコキシ基を、アル
キルアルコキシ基やアルキル基、あるいはジケトン基等
の配位子に置換したものも含む）を採用し、その加水分
解物や、部分加水分解物を含むものを前駆体とする。In the present invention, a silicon alkoxide (a part of an alkoxy group is replaced with an alkylalkoxy group or an alkyl group, (Including those substituted with a ligand such as a diketone group), and those containing a hydrolyzate or a partial hydrolyzate thereof are used as precursors.
【００２３】また、アルミナや酸化硼素、カルシア、マ
グネシア等の原料も、シリカ 100重量部に対し酸化物換
算で20重量部以下の範囲で置換導入でき、それらは、シ
リコンアルコキシド同様の金属アルコキシド化合物や、
酢酸塩、蓚酸塩等の各種有機金属化合物、塩化物、水酸
化物、炭酸塩、硝酸塩等の各種無機金属化合物を採用で
きる。In addition, raw materials such as alumina, boron oxide, calcia and magnesia can be substituted and introduced in a range of 20 parts by weight or less in terms of oxide with respect to 100 parts by weight of silica. ,
Various organic metal compounds such as acetates and oxalates, and various inorganic metal compounds such as chlorides, hydroxides, carbonates and nitrates can be employed.
【００２４】なお、ガラス形成酸化物であり、着色顔料
とのバインディング性に優れ、耐熱性、耐磨耗性、耐薬
品性、耐候性等各種物性にバランスよく優れるシリカは
80重量部以上有するのが望ましい。Silica, which is a glass-forming oxide, has excellent binding properties with a coloring pigment, and is well-balanced in various physical properties such as heat resistance, abrasion resistance, chemical resistance, weather resistance and the like.
It is desirable to have at least 80 parts by weight.
【００２５】黒色系顔料として、酸化銅、酸化マンガ
ン、酸化クロム、酸化鉄、酸化コバルトのうちの少なく
とも２種以上の着色酸化物を含むことにより、良好な無
彩色濃色グレー系の着色膜を形成することができ、また
それらの混在により耐熱性、耐薬品性、耐候性等におい
ても優れた膜を形成できる。By containing at least two coloring oxides of copper oxide, manganese oxide, chromium oxide, iron oxide, and cobalt oxide as a black pigment, a good achromatic dark gray colored film can be obtained. A film excellent in heat resistance, chemical resistance, weather resistance and the like can be formed by mixing them.
【００２６】前記黒色系顔料の平均粒径は５〜50nm程度
であることが好ましい。５nm未満では液中での分散安定
性に乏しく、50nm超過では、膜の平坦、平滑性を損な
い、膜強度が低下し易いという不具合がある。The average particle size of the black pigment is preferably about 5 to 50 nm. If it is less than 5 nm, the dispersion stability in the liquid is poor, and if it exceeds 50 nm, there is a problem that the flatness and smoothness of the film are impaired, and the film strength is liable to decrease.
【００２７】シリカ（シリカ系酸化物）：黒色系顔料
（着色酸化物）の重量比は40：60〜60：40とするもの
で、着色酸化物の割合が60を越えると相対的にガラス質
バインダーを形成するシリカ（シリカ系酸化物）が過小
となり、着色膜が脆化し易く、また膜付着力や膜平坦平
滑性も劣る傾向がある。着色酸化物の割合が40未満であ
ると濃色グレー系の色調を得難く、プライバシー性にお
いて劣る傾向にある。The weight ratio of silica (silica-based oxide) to black-based pigment (colored oxide) should be 40:60 to 60:40. The amount of silica (silica-based oxide) forming the binder becomes too small, the colored film tends to become brittle, and the film adhesion and the flatness of the film tend to be poor. When the ratio of the colored oxide is less than 40, it is difficult to obtain a dark gray color tone, and the privacy tends to be poor.
【００２８】プライバシー性を得るうえで更に重要なフ
ァクターは可視光線透過率であり、その範囲は20〜40％
とする。可視光線透過率が40％を越えると、透視性が増
大し、プライバシー性を維持するのが困難である。また
可視光線透過率が20％未満であると、逆に透視性が阻害
され、窓材としての役割を為し難い。An even more important factor in obtaining privacy is the visible light transmittance, which ranges from 20 to 40%.
And When the visible light transmittance exceeds 40%, transparency increases, and it is difficult to maintain privacy. On the other hand, if the visible light transmittance is less than 20%, on the other hand, the transparency is impaired, and it is difficult to function as a window material.
【００２９】また、光反射によるグレアー感を抑え、目
を刺激せず、周辺環境、特に自然環境と融和、調和させ
るためには、可視光線反射率が10％未満、更に好ましく
は５％以下とするのがよい。In order to suppress glare caused by light reflection, not to irritate the eyes, and to integrate and harmonize with the surrounding environment, particularly the natural environment, the visible light reflectance is less than 10%, more preferably 5% or less. Good to do.
【００３０】上記シリカ系(A) のゾル形成用原料、黒色
系顔料は、アルコール系、エステル系等の有機溶媒に添
加し、更に分散剤としての界面活性剤や、分散助剤、粘
度調整剤としての樹脂を添加する。界面活性剤として
は、アニオン系やノニオン系の界面活性剤がよく、樹脂
としてはセルロース系、ポリビニルアルコール系等の樹
脂が好適に採用できる。The silica-based (A) sol-forming raw material and the black pigment are added to an organic solvent such as an alcohol-based or ester-based solvent, and a surfactant as a dispersant, a dispersing aid, and a viscosity modifier are added. As the resin. As the surfactant, an anionic surfactant or a nonionic surfactant is preferable, and as the resin, a resin such as a cellulose or polyvinyl alcohol resin can be suitably used.
【００３１】これらは各種混合、粉砕手段、例えばボー
ルミル、アトライタ、サンドミル、ホモジナイザー等に
より、充分混合される。特にボールミルは黒色系顔料を
より微粉砕し、均一分散するうえで有効である。These are sufficiently mixed by various mixing and pulverizing means such as a ball mill, an attritor, a sand mill, and a homogenizer. In particular, a ball mill is effective for finely pulverizing and uniformly dispersing a black pigment.
【００３２】次いでこれを塗布液として、ガラス基板上
へ塗布する。塗布手段としてはディップコート、フロー
コート、スピンコート、ロールコート、スプレーコー
ト、スクリーン印刷、フレキソ印刷等の公知手段が採用
でき、適宜マスキングすることにより、例えば自動車の
シェードバンドにおけるような部分的な膜形成は勿論、
任意の形状、図柄に塗膜形成することもできる。Next, this is used as a coating solution and applied onto a glass substrate. Known application methods such as dip coating, flow coating, spin coating, roll coating, spray coating, screen printing, and flexographic printing can be adopted as the application means. By appropriate masking, a partial film such as in an automobile shade band can be used. Of course,
A coating film can be formed in any shape and pattern.
【００３３】塗布後 200〜400 ℃程度、10〜数十分程度
加熱することにより、溶媒や有機物の殆どが飛散した堅
い膜が生成する。但しシリカ（シリカ系酸化物）がバイ
ンダー作用を発揮するうえでは、更に熱処理が必要であ
る。なお、さらに保護膜を積層形成するような場合は、
熱処理は保護膜の熱処理を兼ねて行うのが効率的であ
る。By heating at about 200 to 400 ° C. and about 10 to several tens of minutes after coating, a hard film in which most of the solvent and organic substances are scattered is formed. However, further heat treatment is required for silica (silica-based oxide) to exert a binder effect. In the case where a protective film is further laminated,
It is efficient that the heat treatment is performed also as the heat treatment of the protective film.
【００３４】熱処理は 500〜700 ℃、20〜40分程度かけ
て行うが、例えば２段熱処理とし、低温（500 ℃程度）
熱処理〜高温（700 ℃程度）熱処理等、複数段階で行え
ば、残留気泡や未燃焼カーボン等のない膜をが形成でき
る。The heat treatment is performed at 500 to 700 ° C. for about 20 to 40 minutes. For example, a two-step heat treatment is performed at a low temperature (about 500 ° C.).
By performing the heat treatment in a plurality of stages such as a heat treatment to a high temperature (about 700 ° C.), a film free of residual bubbles, unburned carbon, and the like can be formed.
【００３５】膜厚は熱処理後において 200〜1000nm程度
とするのが望ましく、 200nm未満であると、濃色グレー
系の色調が得難く、可視光線透過率も高きに過ぎてプラ
イバシー性に劣る。他方1000nmを越えると透視性におい
て劣り、また熱処理における曲げ加工に際して、膜の亀
裂や剥離が生じ易い。好適には 200〜500nm 程度とする
のがよい。It is desirable that the film thickness is about 200 to 1000 nm after the heat treatment. If it is less than 200 nm, it is difficult to obtain a dark gray color tone, and the visible light transmittance is too high, resulting in poor privacy. On the other hand, if it exceeds 1000 nm, the transparency is poor, and the film is easily cracked or peeled during bending in the heat treatment. Preferably, the thickness is about 200 to 500 nm.
【００３６】更に好適には、前記ガラス基板上に施した
着色膜用塗布液を加熱乾燥後、引き続き低反射性、耐磨
耗性、耐薬品性、耐候性等に優れる保護膜を形成するの
が望ましい。該保護膜形成のための、シリカ系(B) のゾ
ル用の出発原料の一つとしてはシリコンアルコキシド
（一部のアルコキシ基を、アルキルアルコキシ基やアル
キル基、あるいはジケトン基等の配位子に置換したもの
も含む）を採用し、その加水分解物や、部分加水分解物
を前駆体とする。More preferably, after heating and drying the coating solution for a colored film applied on the glass substrate, a protective film excellent in low reflectivity, abrasion resistance, chemical resistance, weather resistance, etc. is subsequently formed. Is desirable. One of the starting materials for the silica-based (B) sol for forming the protective film is silicon alkoxide (a part of the alkoxy group is converted to an alkyl alkoxy group, an alkyl group, or a ligand such as a diketone group). (Including substituted ones), and its hydrolyzate or partial hydrolyzate is used as a precursor.
【００３７】更に耐磨耗性、耐薬品性、耐候性等を向上
するうえではチタニア、ジルコニア、セリアの１種以上
の原料の導入が必要であり、それらはシリカ 100重量部
に対し酸化物換算で５〜30重量部の範囲で置換導入す
る。それらの出発原料は、酢酸塩、蓚酸塩等の各種有機
金属化合物、塩化物、水酸化物、炭酸塩、硝酸塩等の各
種無機金属化合物であってもよいが、均一分散性の観点
からシリコンアルコキシド同様の金属アルコキシド化合
物を採用するのが好ましい。In order to further improve the abrasion resistance, chemical resistance, weather resistance, etc., it is necessary to introduce one or more kinds of raw materials such as titania, zirconia, and ceria. In the range of 5 to 30 parts by weight. These starting materials may be various organic metal compounds such as acetates and oxalates, and various inorganic metal compounds such as chlorides, hydroxides, carbonates and nitrates, but from the viewpoint of uniform dispersibility, silicon alkoxides may be used. It is preferable to use the same metal alkoxide compound.
【００３８】上記酸化物は、シリカを含めた酸化物中、
５重量部未満では耐磨耗性、耐薬品性、耐候性等の効果
を発揮し得ず、また30重量部を越えるとバインダガラス
形成酸化物としてのシリカが過少となり、膜の密着性が
劣り、また脆化する傾向にある。またチタニア、ジルコ
ニア、セリア等は、シリカより高屈折率であり、反射性
が増大し、更に着色性が生ずる。 これら保護膜用原料
は、着色膜用塗布液調製の場合と同様、アルコール系、
エステル系等の有機溶媒に添加し、更に分散剤としての
界面活性剤や、分散助剤、粘度調整剤としての樹脂を添
加する。界面活性剤としては、アニオン系やノニオン系
の界面活性剤がよく、樹脂としてはセルロース系、ポリ
ビニルアルコール系等の樹脂が好適に採用できる。The above oxides include oxides including silica,
If the amount is less than 5 parts by weight, effects such as abrasion resistance, chemical resistance and weather resistance cannot be exhibited. If the amount exceeds 30 parts by weight, silica as a binder glass forming oxide becomes too small, resulting in poor film adhesion. , And tends to become brittle. Titania, zirconia, ceria, and the like have a higher refractive index than silica, increase reflectivity, and further develop coloring. These protective film raw materials are, as in the case of preparing the coating solution for the colored film, alcohol-based,
It is added to an organic solvent such as an ester, and further, a surfactant as a dispersant, a dispersing aid, and a resin as a viscosity modifier are added. As the surfactant, an anionic surfactant or a nonionic surfactant is preferable, and as the resin, a resin such as a cellulose or polyvinyl alcohol resin can be suitably used.
【００３９】これらは着色膜用塗布液調製の場合と同
様、各種混合、粉砕手段、例えばボールミル、アトライ
タ、サンドミル、ホモジナイザー等により、充分混合さ
れる。次いでこれを塗布液として、加熱乾燥した着色膜
上へ塗布する。塗布手段としてはディップコート、フロ
ーコート、スピンコート、ロールコート、スプレーコー
ト、スクリーン印刷、フレキソ印刷等の公知手段が採用
できる。These are sufficiently mixed by various mixing and pulverizing means, for example, a ball mill, an attritor, a sand mill, a homogenizer, etc., as in the case of preparing the coating liquid for a colored film. Next, this is used as a coating liquid and applied on the heated and dried colored film. Known application methods such as dip coating, flow coating, spin coating, roll coating, spray coating, screen printing, and flexographic printing can be used as the application means.
【００４０】塗布後 200〜400 ℃程度、10〜数十分程度
加熱することにより、溶媒や有機物の殆どが飛散した堅
い膜が生成する。更に前記した如く 500〜700 ℃、20〜
40分程度かけて熱処理するもので、例えば２段熱処理と
し、低温（500 ℃程度）熱処理〜高温（700 ℃程度）熱
処理等、複数段階で行えば、残留気泡や未燃焼カーボン
等のない膜を形成できる。また、膜形成とともに曲げお
よび／または強化加工も兼ねて行うことができる。By heating at about 200 to 400 ° C. for about 10 to several tens of minutes after coating, a hard film with most of the solvent and organic matter scattered is formed. Further, as described above, 500-700 ° C, 20-
Heat treatment is performed for about 40 minutes. For example, a two-step heat treatment is performed, and if a plurality of steps such as a low-temperature (about 500 ° C.) heat treatment to a high-temperature (about 700 ° C.) heat treatment are performed, a film free of residual bubbles and unburned carbon is obtained. Can be formed. In addition, bending and / or strengthening can be performed together with film formation.
【００４１】保護膜の膜厚は熱処理後において 100nm前
後〜 500nm程度であればよく、余りに薄膜であると保護
膜としての作用が不充分となり、他方 500nmを越えると
膜の無色透明性が損なわれる傾向にあり、全体として無
彩色グレー色調が得られ難くなる。また前記着色膜を含
めて1000nmを越えると、熱処理における曲げ加工に際し
て、膜の亀裂や剥離が生じ易い。 上記した如くの保護
膜の形成により、可視光線反射率を５％以下にでき、目
に対する刺激、グレアー感を抑え、周辺環境に対しても
融合調和し易い。The thickness of the protective film may be about 100 nm to about 500 nm after the heat treatment. If the thickness is too small, the function as the protective film is insufficient, and if it exceeds 500 nm, the colorless transparency of the film is impaired. This tends to make it difficult to obtain an achromatic gray tone as a whole. On the other hand, if the thickness exceeds 1000 nm including the colored film, cracks and peeling of the film are likely to occur during bending in heat treatment. By forming the protective film as described above, the visible light reflectance can be reduced to 5% or less, irritation and glare to the eyes can be suppressed, and fusion and harmony with the surrounding environment can be easily achieved.
【００４２】またJIS R 3212に基づくところの耐磨耗性
において、磨耗試験後のヘイズ値（Ｈ％）の、磨耗試験
前のヘイズ値（Ho％）に対する変化量（△Ｈ％）が５％
以下とでき、耐磨耗性、擦傷性に優れる。In the abrasion resistance based on JIS R 3212, the change (ΔH%) between the haze value (H%) after the abrasion test and the haze value (Ho%) before the abrasion test is 5%.
It can be as follows, and is excellent in abrasion resistance and scratch resistance.
【００４３】[0043]
【実施例】以下、実施例により本発明を具体的に説明す
る。ただし本発明はかか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.
【００４４】実施例１ 酸化物換算で，顔料：シリカ（SiO2）＝50：50重量比と
なるように、（Cu,Fe,Mn)O・(Fe、Mn)2O3で示される黒色
系顔料〔ダオピロキサイド＃9550：大日精化工業（株）
製、平均１次粒径約100nm 〕４ｇと、シリコンアルコキ
シド系化合物の加水分解物をアルコール溶媒に溶解した
前駆体溶液（シリカ用原液）〔MS51SG1：三菱化学
（株）製〕25ｇとを、予め界面活性剤よりなる分散剤
〔 DisperBYK＃161 ：ビックケミ− (株) 製〕 0.1ｇを
添加混合したn-ブタノ−ル溶液70ｇの中に添加し、ボ−
ルミルで約20時間粉砕、分散、混合処理することにより
分散溶液を調製し、ボールミル処理後の平均２次粒径が
約10nmである黒色顔料を含む固形分濃度が約８％の分散
液を得た。 Example 1 Black color represented by (Cu, Fe, Mn) O. (Fe, Mn) 2 O 3 so that pigment: silica (SiO 2 ) = 50: 50 weight ratio in oxide conversion Pigment [Daoproxide # 9550: Dainichi Seika Kogyo Co., Ltd.]
4 g of a precursor solution (stock solution for silica) obtained by dissolving a hydrolyzate of a silicon alkoxide compound in an alcohol solvent [MS51SG1: manufactured by Mitsubishi Chemical Corporation], 25 g in advance. A dispersant consisting of a surfactant [DisperBYK # 161: manufactured by Big Chem Co., Ltd.] was added to 70 g of an n-butanol solution mixed with 0.1 g of a surfactant, and the solution was added to a bottle.
A dispersion solution is prepared by pulverizing, dispersing, and mixing with a mill for about 20 hours to obtain a dispersion having a solid content of about 8% including a black pigment having an average secondary particle diameter of about 10 nm after ball milling. Was.
【００４５】この分散液を塗布液として貯留した液槽内
に、片面をマスキングしたガラス基板を浸漬し引き上げ
るディッピング法により塗布し、該被塗布ガラス基板を
約300 ℃で約10分間程度加熱乾燥することにより、膜厚
約 300nmの着色膜付着ガラスを得た。A glass substrate having one side masked is immersed in a liquid tank storing the dispersion as a coating solution, and the glass substrate is dipped and pulled up. The glass substrate to be coated is heated and dried at about 300 ° C. for about 10 minutes. As a result, a glass with a colored film having a thickness of about 300 nm was obtained.
【００４６】次いで、シリコンアルコキシド系化合物の
加水分解物をアルコール溶媒に溶解した前駆体溶液（シ
リカ用原液）〔リクソン：チッソ (株) 製〕を塗布液と
して貯留した液槽内に、上記同様のディッピング法によ
り、上記着色膜の膜面上に塗布し、該被塗布ガラス基板
を約300 ℃で約10分間程度加熱乾燥することにより、着
色膜上に保護膜が付着したガラス基板を得た。Then, a precursor solution (stock solution for silica) in which a hydrolyzate of a silicon alkoxide compound was dissolved in an alcohol solvent (Rixon: manufactured by Chisso Corporation) was stored as a coating solution in a liquid tank similar to the above. A glass substrate having a protective film adhered to the colored film was obtained by applying the film on the surface of the colored film by dipping and heating and drying the glass substrate to be coated at about 300 ° C. for about 10 minutes.
【００４７】得られた保護膜／着色膜からなる積層膜付
着ガラス基板を、さらに約500 ℃で約30分間程度予備熱
処理した後、約 630℃で約３分間熱処理し、急冷して熱
強化した。The glass substrate having the laminated film composed of the protective film / colored film obtained was further preliminarily heat-treated at about 500 ° C. for about 30 minutes, then heat-treated at about 630 ° C. for about 3 minutes, quenched and thermally strengthened. .
【００４８】その結果、総膜厚が約450nm の濃色グレ−
を呈する積層膜形成強化ガラス基板を得た。 該積層膜
形成強化ガラス基板を下記の各項について評価した。 〔光学特性〕：（可視光線透過率、可視光線反射率） JIS R 3106に規定する透過率測定方法、反射率測定方法
に基づき、分光光度計（U 4000型、日立製作所 (株) 製
スペクトロフォトメ−タ−）で波長340 〜1800nmの間の
透過率を測定し、平均可視光線透過率Tv（％）(380〜78
0nm)と平均可視光線反射率Tr（％）(380〜780nm)を求め
た。As a result, a dark gray color having a total film thickness of about 450 nm was obtained.
Was obtained. The following items were evaluated for the laminated glass-formed tempered glass substrate. [Optical characteristics]: (Visible light transmittance, visible light reflectance) Based on the transmittance measurement method and the reflectance measurement method specified in JIS R 3106, a spectrophotometer (U4000, spectrophotometer manufactured by Hitachi, Ltd.) The transmittance between the wavelengths of 340 to 1800 nm was measured by the method (-), and the average visible light transmittance Tv (%) (380 to 78) was measured.
0 nm) and average visible light reflectance Tr (%) (380 to 780 nm).
【００４９】これと合わせ目視により色調観察し、無彩
色の濃色グレー色調を合格とした。 〔耐摩耗性〕：JIS R 3212に規定する耐磨耗性試験方法
に基づき、テーバ−摩耗試験機（摩耗輪CS-10F、荷重50
0gf 、1000回転）により磨耗試験し、試験後のヘイズ値
（Ｈ％）を測定し、試験前のヘイズ値（Ho％）に対する
変化量（△Ｈ％）を求めた。The color tone was visually observed in combination with the above, and an achromatic dark gray color tone was judged to be acceptable. [Abrasion resistance]: Based on the abrasion resistance test method specified in JIS R 3212, a Taber abrasion tester (wear wheel CS-10F, load 50
(0 gf, 1000 rotations), a haze value (H%) after the test was measured, and a change (ΔH%) with respect to the haze value (Ho%) before the test was determined.
【００５０】〔耐薬品性〕：耐酸性；３wt％硫酸（H2SO
4)水溶液を着色膜面に滴下し、常温で約４時間放置後、
外観の変化を目視で評価した。滴下部と、周囲部分の透
過・反射色調に変化が認められず、異常がないものを合
格とした。[Chemical resistance]: Acid resistance; 3 wt% sulfuric acid (H 2 SO
4 ) Drop the aqueous solution on the colored film surface and leave it at room temperature for about 4 hours.
The change in appearance was visually evaluated. No change was observed in the transmission / reflection color tone of the dripping portion and the surrounding portion, and there was no abnormality when the color tone was acceptable.
【００５１】耐アルカリ性；５wt％苛性ソーダ（NaOH）
水溶液を着色膜面に滴下し、常温で約４時間放置後、外
観の変化を目視で評価した。滴下部と周辺部とで違和感
がなく異常がないものを合格とした。Alkali resistance: 5 wt% caustic soda (NaOH)
The aqueous solution was dropped on the surface of the colored film, left at room temperature for about 4 hours, and the appearance change was visually evaluated. A sample having no abnormalities between the dripping portion and the peripheral portion and having no abnormality was accepted.
【００５２】〔耐候性〕 ：部分マスキングしたうえ
で、サンシヤインウエザーメーター（約83℃、降雨無
し）により、約600 時間経過後の外観変化（色調の変
化、泡発生、くもりの発生、膜のひび割れ等）を目視で
評価した。マスキング部との間に違和感がなく異常がな
いものを合格とした。[Weather resistance]: After partial masking, appearance change (change of color tone, generation of bubbles, generation of cloudiness, film formation) after elapse of about 600 hours using a sunshine weather meter (about 83 ° C., no rainfall) And the like) were visually evaluated. Those that did not feel uncomfortable with the masking section and did not have any abnormalities were passed.
【００５３】〔耐煮沸性〕：部分マスキングしたうえ
で、JIS R 3212の耐熱試験方法に基づき、煮沸水に約２
時間浸漬した後、外観を目視で評価した。マスキング部
との間に違和感がなく異常がないものを合格とした。[Boiling resistance]: After partial masking, boiling water was added for about 2 hours based on the heat resistance test method of JIS R3212.
After soaking for an hour, the appearance was visually evaluated. Those that did not feel uncomfortable with the masking section and did not have any abnormalities were passed.
【００５４】その結果、積層膜形成強化ガラス基板は、
図１の光線透過率曲線のグラフ、および表１に示すとお
り、可視光線透過率、可視光線反射率が好適範囲にあ
り、濃色グレー色調を呈してプライバシー性を良好に維
持でき、反射率も極めて低くてグレアー感がなく、また
耐摩耗性を示すヘイズ値の変化量（△Ｈ％）も低く、更
に耐薬品性（耐酸性、耐アルカリ性）、耐候性、耐煮沸
性ともいずれも合格であった。As a result, the laminated glass formation strengthened glass substrate
As shown in the graph of the light transmittance curve of FIG. 1 and Table 1, the visible light transmittance and the visible light reflectance are in a suitable range, a dark gray tone is exhibited, privacy can be maintained well, and the reflectance is also high. Extremely low, no glare, low change in haze value (ΔH%) indicating abrasion resistance, and all chemical resistance (acid resistance, alkali resistance), weather resistance, boiling resistance are all acceptable. there were.
【００５５】実施例２ 酸化物換算で，顔料：シリカ（SiO2）重量比60：40とな
るように、実施例１と同様の黒色系顔料５ｇとシリカ原
液20ｇとを、実施例１同様に予め分散剤 0.1ｇを添加混
合したn-ブタノ−ル溶液75ｇの中に添加し、ボ−ルミル
による粉砕、分散、混合処理をすることにより分散溶液
を調製し、固形分濃度が約８％の黒色系顔料分散液を得
た。 Example 2 5 g of a black pigment similar to that of Example 1 and 20 g of a silica stock solution were used in the same manner as in Example 1 so that the weight ratio of pigment: silica (SiO 2 ) was 60:40 in terms of oxide. A dispersion solution was prepared by adding 0.1 g of a dispersing agent in advance to 75 g of an n-butanol solution mixed and pulverizing, dispersing, and mixing with a ball mill to obtain a solid content of about 8%. A black pigment dispersion was obtained.
【００５６】実施例１と同様、この分散液を塗布液とし
て、ディッピング法によりガラス基板の片面に塗布し、
該被塗布ガラス基板を加熱乾燥することにより、膜厚約
200nmの着色膜付着ガラス基板を得た。In the same manner as in Example 1, this dispersion was applied as a coating liquid to one surface of a glass substrate by a dipping method.
By heating and drying the coated glass substrate, the film thickness is reduced to about
A 200 nm colored glass substrate was obtained.
【００５７】次いで、実施例１同様、保護膜用のシリカ
原液を塗布液として、ディッピング法により上記着色膜
の膜面上に塗布し、該被塗布ガラス基板を加熱乾燥する
ことにより着色膜上に保護膜を付着したガラス基板を得
た。Next, in the same manner as in Example 1, a silica stock solution for a protective film was used as a coating solution and applied on the surface of the colored film by a dipping method, and the coated glass substrate was dried by heating. A glass substrate with a protective film attached was obtained.
【００５８】得られた保護膜／着色膜（積層膜）付着ガ
ラス基板を、実施例１と同様の条件で予備熱処理および
熱処理し熱強化した。その結果、総膜厚が約 350nmの濃
色グレ−を呈する積層膜形成強化ガラス基板を得た。The obtained protective film / colored film (laminated film) -adhered glass substrate was subjected to a preliminary heat treatment and a heat treatment under the same conditions as in Example 1 so as to be thermally strengthened. As a result, a laminated film formation strengthened glass substrate having a dark gray color with a total film thickness of about 350 nm was obtained.
【００５９】該積層膜形成強化ガラス基板を実施例１と
同様に各項について評価した。その結果、表１に示すよ
うに、可視光線透過率、可視光線反射率とも好適範囲内
にあり、濃色グレ−系色調を呈してプライバシー性を良
好に維持でき、グレアー感もなく、また耐摩耗性を示す
ヘイズ値の変化量（△Ｈ％）も低く、更に耐薬品性（耐
酸性、耐アルカリ性）、耐候性、耐煮沸性ともいずれも
合格であった。The laminated glass-formed tempered glass substrate was evaluated for each item in the same manner as in Example 1. As a result, as shown in Table 1, both the visible light transmittance and the visible light reflectance are within the preferred ranges, exhibit a dark gray-based color tone, maintain good privacy, have no glare, and are resistant to glare. The change in haze value (ΔH%) indicating abrasion was low, and all of the chemical resistance (acid resistance and alkali resistance), the weather resistance and the boiling resistance were all acceptable.
【００６０】実施例３ 酸化物換算で，顔料：シリカ（SiO2）＝40：60重量比と
なるように、実施例１と同様な黒色系顔料３ｇとシリカ
原液30ｇとを、予め分散剤 0.1ｇを添加混合したn-ブタ
ノ−ル溶液67ｇの中に添加し、実施例１同様にボ−ルミ
ル処理をすることにより分散溶液を調製し、固形分濃度
が約８％の黒色系顔料分散液を得た。 Example 3 3 g of a black pigment similar to that of Example 1 and 30 g of a silica stock solution were previously added to a dispersant 0.1% so that the weight ratio of pigment: silica (SiO 2 ) = 40: 60 in terms of oxide. g of a black pigment dispersion having a solid content of about 8% by adding the mixture to 67 g of the mixed n-butanol solution and performing ball milling in the same manner as in Example 1. I got
【００６１】実施例１と同様に、この分散液を塗布液と
してディッピング法により、ガラス基板の片面に塗布
し、被塗布ガラス基板を加熱することにより、膜厚約40
0nm の着色膜付着ガラス基板を得た。In the same manner as in Example 1, this dispersion was applied as a coating liquid to one surface of a glass substrate by dipping, and the glass substrate to be coated was heated to a film thickness of about 40%.
A glass substrate with a colored film having a thickness of 0 nm was obtained.
【００６２】次いで、実施例１と同様の保護膜用のシリ
カ原液を塗布液として、実施例１と同様ディッピング法
により上記着色膜面上に塗布し、該被塗布ガラス基板を
加熱することにより着色膜上に保護膜が付着したガラス
基板を得た。Next, the same silica stock solution for the protective film as in Example 1 was used as a coating solution and applied on the surface of the colored film by dipping in the same manner as in Example 1, and the glass substrate to be coated was colored by heating. A glass substrate having a protective film adhered to the film was obtained.
【００６３】得られた保護膜／着色膜（積層膜）付着ガ
ラス基板を、実施例１と同様の条件で、予備熱処理およ
び熱処理し熱強化した。その結果、総膜厚が約500nm の
濃色グレ−を呈する積層膜形成強化ガラス基板を得た。The obtained glass substrate having the protective film / colored film (laminated film) attached thereto was subjected to preliminary heat treatment and heat treatment under the same conditions as in Example 1 so as to be thermally strengthened. As a result, a laminated film-formed glass substrate exhibiting a dark gray color with a total film thickness of about 500 nm was obtained.
【００６４】該積層膜形成強化ガラス基板を実施例１と
同様に各項について評価した。その結果、表１に示すよ
うに、可視光線透過率、可視光線反射率とも好適範囲内
にあり、濃色グレ−系色調を呈してプライバシー性を良
好に維持でき、グレアー感もなく、また耐摩耗性を示す
ヘイズ値の変化量（△Ｈ％）も低く、更に耐薬品性（耐
酸性、耐アルカリ性）、耐候性、耐煮沸性ともいずれも
合格であった。The laminated glass-formed tempered glass substrate was evaluated for each item in the same manner as in Example 1. As a result, as shown in Table 1, both the visible light transmittance and the visible light reflectance are within the preferred ranges, exhibit a dark gray-based color tone, maintain good privacy, have no glare, and are resistant to glare. The change in haze value (ΔH%) indicating abrasion was low, and all of the chemical resistance (acid resistance and alkali resistance), the weather resistance and the boiling resistance were all acceptable.
【００６５】実施例４ 実施例１と同様にガラス基板に着色膜付け処理を施し、
膜厚約300nm の着色膜付着ガラス基板を得た。 Example 4 In the same manner as in Example 1, a glass substrate was subjected to a coloring film forming process.
A glass substrate having a colored film with a thickness of about 300 nm was obtained.
【００６６】次いで、シリコンアルコキシド系化合物に
チタニウムアルコキシド系化合物を混在させアルコール
に溶解したチタニア含有シリカ原液〔MTS-2TI-20、大八
化学工業（株）製、SiO2:TiO2=85:15 重量比〕を調製し
て塗布液とし、実施例１と同様に、ディッピング法によ
り、上記着色膜面上に塗布し、被塗布ガラス基板を加熱
乾燥することにより着色膜上に保護膜を付着したガラス
基板を得た。Next, a titania-containing silica stock solution [MTS-2TI-20, manufactured by Daihachi Chemical Industry Co., Ltd., SiO 2 : TiO 2 = 85: 15, in which a titanium alkoxide compound is mixed with a silicon alkoxide compound and dissolved in alcohol. [Weight ratio] to prepare a coating solution, and the coating solution was applied on the surface of the colored film by a dipping method in the same manner as in Example 1, and the glass substrate to be coated was heated and dried to attach a protective film on the colored film. A glass substrate was obtained.
【００６７】得られた保護膜／着色膜（積層膜）付着ガ
ラス基板を、実施例１と同様の条件で、予備熱処理およ
び熱処理し、熱強化した。その結果、総膜厚が約550nm
の濃色グレ−を呈する積層膜形成強化ガラス基板を得
た。The obtained protective film / colored film (laminated film) -adhered glass substrate was subjected to a preliminary heat treatment and a heat treatment under the same conditions as in Example 1 so as to be thermally strengthened. As a result, the total film thickness is about 550 nm
To obtain a laminated glass-formed tempered glass substrate having a dark gray color.
【００６８】該積層膜形成強化ガラス基板を実施例１と
同様に各項について評価した。その結果、表１に示すよ
うに、可視光線透過率、可視光線反射率とも好適範囲内
にあり、濃色グレ−系色調を呈してプライバシー性を良
好に維持でき、グレアー感もなく、また耐摩耗性を示す
ヘイズ値の変化量（△Ｈ％）も低く、更に耐薬品性（耐
酸性、耐アルカリ性）、耐候性、耐煮沸性ともいずれも
合格であった。The laminated glass-formed tempered glass substrate was evaluated for each item in the same manner as in Example 1. As a result, as shown in Table 1, both the visible light transmittance and the visible light reflectance are within the preferred ranges, exhibit a dark gray-based color tone, maintain good privacy, have no glare, and are resistant to glare. The change in haze value (ΔH%) indicating abrasion was low, and all of the chemical resistance (acid resistance and alkali resistance), the weather resistance and the boiling resistance were all acceptable.
【００６９】実施例５ 実施例１と同様にガラス基板に着色膜付け処理を施し、
膜厚約300nm の着色膜付着ガラス基板を得た。 Example 5 As in Example 1, a glass substrate was subjected to a coloring film forming process.
A glass substrate having a colored film with a thickness of about 300 nm was obtained.
【００７０】次いで、シリコンアルコキシド系化合物に
ジルコニウムアルコキシド系化合物を混在させアルコー
ルに溶解したジルコニア含有シリカ原液〔CG19ZR10、大
八化学工業（株）製、SiO2:ZrO2=75:25 重量比〕を調製
して塗布液とし、実施例１と同様に、ディッピング法に
より、上記着色膜面上に塗布し、被塗布ガラス基板を加
熱することにより、着色膜上に保護膜を付着したガラス
基板を得た。Next, a zirconia-containing silica stock solution (CG19ZR10, manufactured by Daihachi Chemical Industry Co., Ltd., SiO 2 : ZrO 2 = 75: 25 weight ratio) was prepared by mixing a zirconium alkoxide compound with a silicon alkoxide compound and dissolving in alcohol. A glass substrate having a protective film adhered on the colored film by preparing the coating solution and applying the solution on the surface of the colored film by a dipping method in the same manner as in Example 1 and heating the glass substrate to be coated. Was.
【００７１】得られた保護膜／着色膜（積層膜）付着ガ
ラス基板を、実施例１と同様の条件で、予備熱処理およ
び熱処理し熱強化した。その結果、総膜厚が約500nm の
濃色グレ−を呈する積層膜形成強化ガラス基板を得た。The glass substrate having the protective film / colored film (laminated film) attached thereto was subjected to a preliminary heat treatment and a heat treatment under the same conditions as in Example 1 so as to be thermally strengthened. As a result, a laminated film-formed glass substrate exhibiting a dark gray color with a total film thickness of about 500 nm was obtained.
【００７２】該積層膜形成強化ガラス基板を実施例１と
同様に各項について評価した。その結果、表１に示すよ
うに、可視光線透過率、可視光線反射率とも好適範囲内
にあり、濃色グレ−系色調を呈してプライバシー性を良
好に維持でき、グレアー感もなく、また耐摩耗性を示す
ヘイズ値の変化量（△Ｈ％）も低く、更に耐薬品性（耐
酸性、耐アルカリ性）、耐候性、耐煮沸性ともいずれも
合格であった。The laminated glass-formed tempered glass substrate was evaluated for each item in the same manner as in Example 1. As a result, as shown in Table 1, both the visible light transmittance and the visible light reflectance are within the preferred ranges, exhibit a dark gray-based color tone, maintain good privacy, have no glare, and are resistant to glare. The change in haze value (ΔH%) indicating abrasion was low, and all of the chemical resistance (acid resistance and alkali resistance), the weather resistance and the boiling resistance were all acceptable.
【００７３】実施例６ 実施例１で用いた顔料を（Cu、Cr、Mn)O・(Cu、Cr)2O3で
示される黒色系顔料〔ダオピロキサイド＃3510、大日精
化工業（株）製〕に変更した以外は、実施例１と同様に
着色膜付け処理して膜厚約350nm の着色膜付着ガラス基
板を得た。 Example 6 The pigment used in Example 1 was changed to a black pigment represented by (Cu, Cr, Mn) O. (Cu, Cr) 2 O 3 [Daoproxide # 3510, Dainichi Seika Kogyo Co., Ltd. )), Except that a glass substrate having a color film-adhered film having a thickness of about 350 nm was obtained in the same manner as in Example 1.
【００７４】次いで、実施例１と同様の保護膜用シリカ
原液を塗布液として、実施例１と同様に、ディッピング
法により上記着色膜面上に塗布し、被塗布ガラス基板を
加熱することにより着色膜上に保護膜を付着したガラス
基板を得た。Next, the same silica stock solution for the protective film as in Example 1 was used as a coating solution, and applied onto the surface of the colored film by dipping in the same manner as in Example 1, and the glass substrate to be coated was colored by heating. A glass substrate having a protective film adhered on the film was obtained.
【００７５】得られた保護膜／着色膜（積層膜）付着ガ
ラス基板を、実施例１と同様の条件で、予備熱処理およ
び熱処理し、熱強化した。その結果、総膜厚が約500nm
の濃色グレ−を呈する積層膜形成強化ガラス基板を得
た。The obtained protective film / colored film (laminated film) -adhered glass substrate was subjected to a preliminary heat treatment and a heat treatment under the same conditions as in Example 1 to be thermally strengthened. As a result, the total film thickness is about 500 nm
To obtain a laminated glass-formed tempered glass substrate having a dark gray color.
【００７６】該積層膜形成強化ガラス基板を実施例１と
同様に各項について評価した。その結果、表１に示すよ
うに、可視光線透過率、可視光線反射率とも好適範囲内
にあり、濃色グレ−系色調を呈してプライバシー性を良
好に維持でき、グレー感もなく、また耐摩耗性を示すヘ
イズ値の変化量（△Ｈ％）も低く、更に耐薬品性（耐酸
性、耐アルカリ性）、耐候性、耐煮沸性ともいずれも合
格であった。The laminated glass-formed tempered glass substrate was evaluated for each item in the same manner as in Example 1. As a result, as shown in Table 1, both the visible light transmittance and the visible light reflectance are within the preferred ranges, exhibit a dark gray-based color tone, maintain good privacy, have no gray feeling, and are resistant to gray. The change in haze value (ΔH%) indicating abrasion was low, and all of the chemical resistance (acid resistance and alkali resistance), the weather resistance and the boiling resistance were all acceptable.
【００７７】実施例７ 実施例３とほぼ同様にガラス基板に着色膜付け処理を施
し、膜厚約530nm の着色膜付着ガラス基板を得た。 Example 7 A glass substrate was treated with a colored film almost in the same manner as in Example 3 to obtain a colored film-adhered glass substrate having a thickness of about 530 nm.
【００７８】次いで、得られた着色膜付着ガラス基板
を、600℃で30分間熱処理すると共に熱曲げ加工するこ
とにより、濃色グレ−を呈する着色膜形成曲げガラス基
板を得、該着色膜形成曲げガラス基板を実施例１と同様
に各項について評価した。Next, the obtained glass substrate with a colored film is subjected to a heat treatment at 600 ° C. for 30 minutes and is subjected to a heat bending process, thereby obtaining a bent glass substrate with a colored film showing a dark gray. The glass substrate was evaluated for each item in the same manner as in Example 1.
【００７９】その結果、表１に示すように、可視光線透
過率、可視光線反射率とも好適範囲内にあり、濃色グレ
−系色調を呈してプライバシー性を良好に維持でき、濃
色グレ−系色調を呈してプライバシー性を良好に維持で
き、グレアー感も弱い。なお、保護膜を被覆していない
ため、耐摩耗性を示すヘイズ値の変化量（△Ｈ％）は上
記実施例より若干高いが、耐薬品性（耐酸性、耐アルカ
リ性）、耐候性、耐煮沸性においては問題はない。As a result, as shown in Table 1, both the visible light transmittance and the visible light reflectance were within the preferred ranges, the color tone was dark, the privacy was satisfactorily maintained, and the dark color was maintained. It can maintain good privacy due to its color tone and has a weak glare. Since the protective film was not covered, the change in haze value (ΔH%) indicating abrasion resistance was slightly higher than that in the above example, but the chemical resistance (acid resistance and alkali resistance), weather resistance, and There is no problem in boiling.
【００８０】比較例１ 酸化物換算で，顔料：シリカ（SiO2）＝70：30重量比と
なるように、実施例１と同様な黒色系顔料６ｇとシリカ
原液15ｇとを、予め実施例１と同様な分散剤 0.1ｇを添
加混合したn-ブタノ−ル溶液79ｇの中に添加し、実施例
１と同様にボ−ルミル処理することにより分散溶液を調
製し、固形分濃度が約８％の黒色系顔料分散液を得た。 Comparative Example 1 6 g of a black pigment similar to that of Example 1 and 15 g of a silica stock solution were previously prepared in Example 1 so that the pigment: silica (SiO 2 ) = 70: 30 weight ratio in terms of oxide was obtained. A dispersion solution was prepared by adding 0.1 g of the same dispersant as described above to 79 g of a mixed n-butanol solution, and performing ball milling in the same manner as in Example 1 to give a solid content of about 8%. Was obtained.
【００８１】更に実施例１と同様に、この分散液を塗布
液としてディッピング法により、ガラス基板の片面に塗
布し、該被塗布ガラス基板を加熱乾燥することにより、
膜厚約150nm の着色膜が付着したガラス基板を得た。ち
なみに、その可視光線透過率は約25％程度であった。Further, in the same manner as in Example 1, this dispersion was applied as a coating liquid to one surface of a glass substrate by dipping, and the glass substrate to be coated was dried by heating.
A glass substrate having a colored film with a thickness of about 150 nm was obtained. Incidentally, its visible light transmittance was about 25%.
【００８２】次いで、実施例１と同様に保護膜用シリカ
原液を塗布液として、ディッピング法により上記着色膜
面上に塗布し、該被塗布ガラス基板を加熱することによ
り着色膜上に保護膜を付着したガラス基板を得た。Next, in the same manner as in Example 1, a silica stock solution for a protective film was used as a coating solution and applied onto the colored film surface by a dipping method, and the coated glass substrate was heated to form a protective film on the colored film. A glass substrate was obtained.
【００８３】得られた保護膜／着色膜（積層膜）付着ガ
ラス基板を、実施例１と同様の条件で、予備熱処理およ
び熱処理し熱強化した。その結果、総膜厚が約300nm の
積層膜形成強化ガラス基板を得た。The glass substrate having the protective film / colored film (laminated film) attached thereto was subjected to a preliminary heat treatment and a heat treatment under the same conditions as in Example 1 so as to be thermally strengthened. As a result, a laminated glass formation strengthened glass substrate having a total film thickness of about 300 nm was obtained.
【００８４】該積層膜形成強化ガラス基板を実施例１と
同様に各項について評価した。その結果、表１に示すよ
うに、可視光線透過率、可視光線反射率とも実施例と近
似しており、濃色グレー系色調を呈していたが、すでに
膜にクラックが多数発生しており、耐摩耗性試験におい
て、約1000回転後には、積層膜は完全に剥離していた。The laminated glass-formed tempered glass substrate was evaluated for each item in the same manner as in Example 1. As a result, as shown in Table 1, both the visible light transmittance and the visible light reflectance were similar to those of the example and exhibited a dark gray color tone, but many cracks had already occurred in the film, In the abrasion resistance test, the laminated film was completely peeled off after about 1000 rotations.
【００８５】また、耐薬品性（耐酸性、耐アルカリ性）
および耐煮沸性については合格の範疇にはあるが、耐候
性試験においては、積層膜は上記と同様の剥離現象が見
られ、プライバシーガラスとして到底使用し得ないもの
である。Also, chemical resistance (acid resistance, alkali resistance)
Although the boiling resistance is within the acceptable range, in a weather resistance test, the laminated film exhibits the same peeling phenomenon as described above and cannot be used as privacy glass at all.
【００８６】比較例２ 酸化物換算で，顔料：シリカ（SiO2）＝30：70重量比と
なるように、実施例１と同様の黒色系顔料２ｇとシリカ
原液35ｇとを、予め実施例１と同様な分散剤 0.1ｇを添
加混合したn-ブタノ−ル溶液63ｇの中に添加し、実施例
１と同様にボ−ルミル処理をすることにより分散溶液を
調製し、固形分濃度が約８％の黒色系顔料分散液を得
た。 Comparative Example 2 2 g of a black pigment similar to that of Example 1 and 35 g of a silica stock solution were previously prepared in Example 1 so that the weight ratio of pigment to silica (SiO 2 ) was 30:70 in terms of oxide. 0.1 g of the same dispersant was added to 63 g of an n-butanol solution mixed and subjected to ball milling in the same manner as in Example 1 to prepare a dispersion solution having a solid content of about 8%. % Of a black pigment dispersion.
【００８７】更に実施例１と同様に、この分散液を塗布
液としてディッピング法により、ガラス基板の片面に塗
布し、該被塗布ガラス基板を加熱乾燥することにより、
膜厚約600nm の着色膜を付着したガラス基板を得た。ち
なみに、その可視光線透過率は約25％程度であった。Further, in the same manner as in Example 1, this dispersion was applied as a coating liquid to one surface of a glass substrate by dipping, and the glass substrate to be coated was dried by heating.
A glass substrate having a colored film having a thickness of about 600 nm was obtained. Incidentally, its visible light transmittance was about 25%.
【００８８】次いで、実施例１と同様に保護膜用シリカ
原液を塗布液として、ディッピング法により上記着色膜
面上に塗布し、該被塗布ガラス基板を加熱することによ
り着色膜上に保護膜を付着したガラス基板を得た。Next, a silica stock solution for a protective film was used as a coating solution in the same manner as in Example 1 to apply the solution onto the colored film surface by dipping, and the glass substrate to be coated was heated to form a protective film on the colored film. A glass substrate was obtained.
【００８９】得られた保護膜／着色膜（積層膜）付着ガ
ラス基板を、実施例１と同様の条件で、予備熱処理およ
び熱処理し強化した。その結果、総膜厚が約800nm の積
層膜形成強化ガラス基板を得た。The obtained protective film / colored film (laminated film) -adhered glass substrate was reinforced by preliminary heat treatment and heat treatment under the same conditions as in Example 1. As a result, a laminated film formation strengthened glass substrate having a total film thickness of about 800 nm was obtained.
【００９０】該積層膜付き強化ガラス基板を実施例１と
同様に各項について評価した。その結果、表１に示すよ
うに、可視光線透過率、可視光線反射率とも実施例と近
似しており、濃色グレー系色調を呈していたが、すでに
膜全面にクラックが多数発生しており、耐摩耗性試験に
おいて、約1000回転後には、積層膜は完全に剥離してい
た。The tempered glass substrate with the laminated film was evaluated for each item in the same manner as in Example 1. As a result, as shown in Table 1, both the visible light transmittance and the visible light reflectance were similar to those of the example, and they exhibited a dark gray color tone, but many cracks had already occurred on the entire surface of the film. In the abrasion resistance test, the laminated film was completely peeled after about 1000 rotations.
【００９１】また、耐薬品性（耐酸性、耐アルカリ性）
についてはクラックがますます拡大、発達して各所に剥
離状態が観察された。さらに耐煮沸性、耐候性試験にお
いては、積層膜は耐磨耗性試験と同様の剥離現象が見ら
れ、プライバシーガラスとして到底使用し得ないもので
ある。Also, chemical resistance (acid resistance, alkali resistance)
As for the cracks, cracks were further expanded and developed, and peeling states were observed at various places. Furthermore, in the boiling resistance and weather resistance tests, the laminated film shows the same peeling phenomenon as the abrasion resistance test, and cannot be used as privacy glass at all.
【００９２】 〔表１〕 透過率 反射率 外観 耐磨耗 耐酸性 耐アルカリ 耐候性 耐煮沸 （％） （％） 色調 性(%) 性 性 実施例１ 26.0 4.6 ○ 3.8 ○ ○ ○ ○ 実施例２ 24.6 4.5 ○ 4.2 ○ ○ ○ ○ 実施例３ 26.7 4.3 ○ 4.5 ○ ○ ○ ○ 実施例４ 27.1 4.5 ○ 3.9 ○ ○ ○ ○ 実施例５ 26.3 4.7 ○ 3.5 ○ ○ ○ ○ 実施例６ 28.1 4.3 ○ 4.1 ○ ○ ○ ○ 実施例７ 25.5 7.0 ○ 7.5 ○ ○ ○ ○ 比較例１ 26.6 4.6 クラック 膜剥離 ○ ○ 膜剥離 ○ 比較例２ 27.2 4.0 クラック 膜剥離 クラック拡 クラック拡 膜剥離 膜剥離 大.剥離 大.剥離 注）透過率：平均可視光線透過率 反射率：平均可視光線反射率 外観色調、耐酸性、耐アルカリ性、耐候性、耐煮沸性：合格----○ 耐磨耗性：ヘイズ値（％）の変化量（△Ｈ％）[Table 1] Transmittance Reflectivity Appearance Abrasion resistance Acid resistance Alkali resistance Weather resistance Boiling resistance (%) (%) Color tone (%) Property Example 1 26.0 4.6 ○ 3.8 ○ ○ ○ ○ Example 2 24.6 4.5 ○ 4.2 ○ ○ ○ ○ Example 3 26.7 4.3 ○ 4.5 ○ ○ ○ ○ Example 4 27.1 4.5 ○ 3.9 ○ ○ ○ ○ Example 5 26.3 4.7 ○ 3.5 ○ ○ ○ ○ Example 6 28.1 4.3 ○ 4.1 ○ ○ ○ ○ Example 7 25.5 7.0 ○ 7.5 ○ ○ ○ ○ Comparative Example 1 26.6 4.6 Crack film peeling ○ ○ Film peeling ○ Comparative Example 2 27.2 4.0 Crack film peeling Crack expansion Crack expanding film peeling Large peeling Large peeling Note) Transmittance: average visible light transmittance Reflectance: average visible light reflectance Appearance color tone, acid resistance, alkali resistance, weather resistance, boiling resistance: pass ---- ○ Abrasion resistance: change in haze value (%) Amount (△ H%)
【００９３】[0093]
【発明の効果】以上、本発明のガラスは、濃色グレ−系
の色調で、所望する遮光状態と適度な透視性を示し、プ
ライバシーガラスとして好適であり、光反射は低くグレ
アー感は抑えられ、周辺環境とも融合調和し易く、耐薬
品性、耐煮沸性、耐摩耗性等耐久性に優れ、大面積ガラ
ス基板でも高い品質を確保することができ、建築用窓
材、自動車など車両用窓材、船舶、航空機など輸送機用
窓材等として単板でも充分に適用できる等、各種ガラス
物品にも広く採用し得る。またその製法も簡便かつ効率
的で、曲げ強化も能率的に行えるという効果を奏する。As described above, the glass of the present invention has a dark gray color tone, exhibits a desired light-shielding state and appropriate transparency, is suitable as a privacy glass, has low light reflection and suppresses glare. It is easy to integrate with the surrounding environment, and has excellent durability such as chemical resistance, boiling resistance, and abrasion resistance. It can ensure high quality even with large-area glass substrates. It can be widely applied to various glass articles, for example, a single plate can be sufficiently applied as a material, a window material for a transport machine such as a ship or an aircraft, and the like. In addition, the manufacturing method is simple and efficient, and an effect that bending can be efficiently performed can be achieved.
【図１】本発明の実施例１のプライバシ−ガラス、およ
び未膜付ガラス基板における透過率曲線を示すグラフで
あり、実線は本発明実施例１のガラス基板、点線は未膜
のガラス基板である。FIG. 1 is a graph showing transmittance curves of a privacy glass of Example 1 of the present invention and a glass substrate with an uncoated film, wherein a solid line represents a glass substrate of Example 1 of the present invention, and a dotted line represents an uncoated glass substrate. is there.
Claims (7)
色性の酸化物成分からなる黒色系顔料を分散したシリカ
系(A) のゾルを前躯体とする、濃色グレ−系の着色膜を
形成してなるプライバシ−ガラスであって、その可視光
線透過率が20〜40％、可視光線反射率が10％未満である
ことを特徴とするプライバシーガラス。1. A dark-gray coloring system comprising a precursor of a silica-based (A) sol in which a black pigment composed of two or more coloring oxide components is dispersed on the surface of a transparent glass substrate. A privacy glass comprising a film, wherein the privacy glass has a visible light transmittance of 20 to 40% and a visible light reflectance of less than 10%.
シリカとMeOx（Me＝Al, Ca, Mg, B の１種以上）の混合
ゾルからなり、シリカ：MeOxの重量比が80：20〜 100：
０であることを特徴とする請求項１記載のプライバシー
ガラス。2. The silica-based (A) sol comprises silica or a mixed sol of silica and MeOx (Me = at least one of Al, Ca, Mg, B), and a silica: MeOx weight ratio of 80: 20-100:
The privacy glass according to claim 1, wherein the value is 0.
化物重量比が40：60〜60：40であることを特徴とする請
求項１または２記載のプライバシーガラス。3. The privacy glass according to claim 1, wherein the weight ratio of the silica-based (A) oxide to the black pigment is 40:60 to 60:40.
着色膜の上に、シリカ系(B) のゾルを前躯体とする保護
膜を形成してなることを特徴とする請求項１記載のプラ
イバシ−ガラス。4. A protective film having a silica (B) sol as a precursor is formed on a dark gray colored film applied to a transparent glass substrate. Privacy glass.
＝Ti, Zr, Ceの１種以上）の混合ゾルからなり、シリ
カ：MO2 の重量比が70：30〜95：５であることを特徴と
する請求項４記載のプライバシーガラス。5. A silica-based (B) sol comprising silica and MO 2 (M
= Ti, Zr, consists mixed sol of one or more Ce), silica weight ratio of MO 2 is 70: 30 to 95: 5 in claim 4 wherein the privacy glass, characterized in that.
造するにあたり、 (a) 透明ガラス基板を用意する工程と、 (b) 黒色系顔料：シリカ系(A) のゾルの酸化物重量比が
40〜60：60〜40となるべく調合した、黒色系顔料と、シ
リカ系(A) のゾル用出発原料とを、分散剤と溶媒とを含
む液に添加し、撹拌混合して塗布液を調製する工程と、 (c) 前記塗布液を、前記ガラス基板表面上に塗布し、加
熱乾燥して膜を付着する工程と、 (d）更に熱処理して成膜する工程と、によってガラス基
板面上に着色膜を形成することを特徴とするプライバシ
−ガラスの製法。6. A method for producing the privacy glass according to claim 1, wherein: (a) a step of preparing a transparent glass substrate; and (b) a black pigment: silica-based (A) sol having an oxide weight ratio of:
40-60: The black pigment and silica-based (A) sol starting material prepared to be 60-40 are added to a solution containing a dispersant and a solvent, and the mixture is stirred and mixed to prepare a coating solution. (C) applying the coating solution on the glass substrate surface, heating and drying to deposit a film, and (d) further heat-treating to form a film. A method for producing privacy glass, characterized in that a colored film is formed on the substrate.
ガラス基板上に施した着色膜用塗布液を加熱乾燥後、引
き続き保護膜を形成するにあたり、 (e) シリカ系(B) のゾルにおけるシリカ：MO2 の重量比
が70：30〜95：５となるべくシリカ系(B) のゾル用出発
を、分散剤と溶媒とを含む液に添加し、撹拌混合して塗
布液を調製する工程と、 (f) 前記塗布液を前記ガラス基板表面上に塗布し、加熱
乾燥して膜を付着する工程と、 (g) 更に熱処理して成膜する工程と、によって着色膜面
上に保護膜を形成することを特徴とするプライバシ−ガ
ラスの製法。7. The method according to claim 6 (a) to (c),
After heating and drying the coating solution for the colored film applied on the glass substrate, the protective film is successively formed. (E) The silica (B) sol has a weight ratio of silica: MO 2 of 70:30 to 95: 5. Adding a silica-based (B) sol starting solution to a liquid containing a dispersant and a solvent as much as possible, stirring and mixing to prepare a coating solution, and (f) coating the coating solution on the glass substrate surface. A method for producing privacy glass, comprising forming a protective film on a colored film surface by the steps of applying, heating and drying to deposit a film, and (g) further heat-treating to form a film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9112072A JPH10297938A (en) | 1997-04-30 | 1997-04-30 | Privacy glass and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9112072A JPH10297938A (en) | 1997-04-30 | 1997-04-30 | Privacy glass and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10297938A true JPH10297938A (en) | 1998-11-10 |
Family
ID=14577377
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9112072A Pending JPH10297938A (en) | 1997-04-30 | 1997-04-30 | Privacy glass and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10297938A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008536791A (en) * | 2005-04-19 | 2008-09-11 | ショット アクチエンゲゼルシャフト | Glass with decorative coating, or glass-ceramic product |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04182327A (en) * | 1990-11-15 | 1992-06-29 | Asahi Glass Co Ltd | Surface-treated glass and its production |
| JPH05805A (en) * | 1991-06-20 | 1993-01-08 | Sumitomo Electric Ind Ltd | Thin film formation by a sol-gel method |
| JPH054839A (en) * | 1991-06-20 | 1993-01-14 | Sumitomo Electric Ind Ltd | Method for preparing thin film by sol-gel method |
| JPH08104544A (en) * | 1994-09-30 | 1996-04-23 | Central Glass Co Ltd | Heat ray reflecting and ultraviolet ray absorbing glass and its production |
| JPH08253348A (en) * | 1995-01-20 | 1996-10-01 | Carl Zeiss:Fa | Glass image face for cathode ray tube with adjustable spectrum permeability and its method for manufacturing |
| JPH0930836A (en) * | 1995-02-27 | 1997-02-04 | Central Glass Co Ltd | Glass with light screening film and its production |
-
1997
- 1997-04-30 JP JP9112072A patent/JPH10297938A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04182327A (en) * | 1990-11-15 | 1992-06-29 | Asahi Glass Co Ltd | Surface-treated glass and its production |
| JPH05805A (en) * | 1991-06-20 | 1993-01-08 | Sumitomo Electric Ind Ltd | Thin film formation by a sol-gel method |
| JPH054839A (en) * | 1991-06-20 | 1993-01-14 | Sumitomo Electric Ind Ltd | Method for preparing thin film by sol-gel method |
| JPH08104544A (en) * | 1994-09-30 | 1996-04-23 | Central Glass Co Ltd | Heat ray reflecting and ultraviolet ray absorbing glass and its production |
| JPH08253348A (en) * | 1995-01-20 | 1996-10-01 | Carl Zeiss:Fa | Glass image face for cathode ray tube with adjustable spectrum permeability and its method for manufacturing |
| JPH0930836A (en) * | 1995-02-27 | 1997-02-04 | Central Glass Co Ltd | Glass with light screening film and its production |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008536791A (en) * | 2005-04-19 | 2008-09-11 | ショット アクチエンゲゼルシャフト | Glass with decorative coating, or glass-ceramic product |
| US8329302B2 (en) | 2005-04-19 | 2012-12-11 | Schott Ag | Glass or glass-ceramic articles with decorative coating |
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