JPH07330379A - Colored transparent material - Google Patents
Colored transparent materialInfo
- Publication number
- JPH07330379A JPH07330379A JP11915494A JP11915494A JPH07330379A JP H07330379 A JPH07330379 A JP H07330379A JP 11915494 A JP11915494 A JP 11915494A JP 11915494 A JP11915494 A JP 11915494A JP H07330379 A JPH07330379 A JP H07330379A
- Authority
- JP
- Japan
- Prior art keywords
- film
- colored
- glass
- transparent
- fine particles
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、着色膜を設けた透明体
に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent body provided with a colored film.
【０００２】[0002]
【従来の技術】近年、自動車ガラスには、快適さ、空調
負荷低減、車内のプライバシーを得ること等を目的とし
て様々な熱線反射被膜や着色膜がコートされたものが使
用されている。従来、運転視界域外のリアサイドガラ
ス、バックライト等には、可視光線透過率が７０％以下
のいわゆる濃色ガラスが多く採用されてきた。この濃色
ガラスは太陽光線遮蔽性能が高いことによる室内の快適
性や空調負荷低減、高級感を与える色調の選択が可能、
デザイン的に優れた意匠性、車内のプライバシー保護、
等の面で優れている。2. Description of the Related Art In recent years, automotive glass coated with various heat ray reflective coatings and colored coatings has been used for the purpose of comfort, reduction of air conditioning load, privacy in the vehicle, and the like. Conventionally, so-called dark-colored glass having a visible light transmittance of 70% or less has been often used for rear side glasses, backlights, and the like outside the driving field of view. This dark-colored glass has high sunlight shielding performance, which makes it possible to reduce indoor comfort and air-conditioning load, and to select a color tone that gives a sense of luxury.
Excellent design, privacy protection in the car,
Etc. are excellent.
【０００３】これらのガラスの従来からある製法とし
て、フロートバスから出てきたまだ熱いガラスリボンに
熱線反射被膜を形成し得る化合物を含む溶液を吹き付け
焼き付けるオンラインスプレー法や、真空成膜装置内で
物理的に成膜するスパッタリング法、メッシュスクリー
ンをを用いて印刷するスクリーン印刷法、ロールに一度
伸ばした溶液を転写するフレキソ印刷法、溶液に漬けて
引き上げるディップ法等がある。この中でオンラインス
プレー法、スパッタリング法で作られた膜では、比較的
強固な膜を形成可能であるが、耐久性や耐摩耗性の面で
優れた膜材料はかなり限定されている。Conventional methods for producing these glasses include an online spray method in which a solution containing a compound capable of forming a heat ray reflective coating is sprayed and baked onto a still hot glass ribbon emerging from a float bath, and a physical method in a vacuum film forming apparatus. There are a sputtering method for forming a film dynamically, a screen printing method for printing using a mesh screen, a flexo printing method for transferring a solution once stretched on a roll, a dipping method for dipping in a solution. Among them, a film formed by an online spray method or a sputtering method can form a relatively strong film, but the film material excellent in durability and abrasion resistance is considerably limited.
【０００４】[0004]
【発明が解決しようとする課題】一方、スクリーン印刷
法、フレキソ印刷法、ディップ法等のいわゆる湿式（ウ
ェット）法で成膜された膜は後加熱をするとかなり膜が
強固になる。しかし、これらの膜には、溶媒が蒸発して
体積が減ったことによる内部空洞や、粘性を持たせるた
めに添加してある樹脂成分が加熱処理でガス化し飛び出
したクレーター状の穴が存在するため膜の堅牢度が下が
る。On the other hand, a film formed by a so-called wet method such as a screen printing method, a flexographic printing method and a dip method becomes considerably strong when it is post-heated. However, these films have internal cavities due to the evaporation of the solvent and a decrease in volume, and crater-shaped holes in which the resin component added to give viscosity is gasified by the heat treatment and popped out. Therefore, the fastness of the film is reduced.
【０００５】すなわち、上述のウェット法等で成膜され
た膜は５００〜７００℃の高温後処理を施すため、残留
焼き付き成分はＴｉＯ2 、ＳｉＯ2 、ＺｒＯ2 、Ｔａ2
Ｏ3等の比較的安定な酸化物や、その中に分散したＡ
ｕ、Ｐｔ、Ｐｄ、Ａｇ等の高温後処理でも酸化されない
貴金属等の微粒子などが主であるが、後加熱により膜の
堅牢度が下がり、膜中の空孔の存在と合わせて自動車用
窓ガラスには使用し難かった。That is, since the film formed by the above-mentioned wet method or the like is subjected to a high temperature post-treatment at 500 to 700 ° C., residual seizure components are TiO 2 , SiO 2 , ZrO 2 , Ta 2
A relatively stable oxide such as O 3 or A dispersed in it
Mainly fine particles of noble metals and the like that are not oxidized even after high-temperature post-treatment of u, Pt, Pd, Ag, etc., but the fastness of the film is lowered by post-heating, and the presence of pores in the film causes window glass for automobiles. Was difficult to use.
【０００６】本発明は、機械的強度、耐擦傷性、耐摩耗
性、耐候性および耐薬品性に優れた着色膜が形成されて
いて、該膜が露出した単板状態で使用することが可能な
自動車用窓ガラスの提供を目的とするものである。According to the present invention, a colored film having excellent mechanical strength, scratch resistance, abrasion resistance, weather resistance and chemical resistance is formed, and the film can be used in a single plate state with the film exposed. The purpose of the present invention is to provide window glass for automobiles.
【０００７】[0007]
【課題を解決するための手段】本発明は前述の課題を解
決するためになされたものであり、透明基板上に、Ｔ
ｉ、Ｓｉ、Ｚｒ、Ｔａ、ＳｎおよびＺｎからなる群から
選ばれる少なくとも１種の金属の酸化物を主成分とする
膜中に、金属および／または金属酸化物の微粒子が分散
した着色膜と、該着色膜を覆って膜厚０．１μｍ以上２
００μｍ以下の透明保護膜とが設けられた着色透明体を
提供するものである。SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems.
a colored film in which fine particles of a metal and / or a metal oxide are dispersed in a film containing an oxide of at least one metal selected from the group consisting of i, Si, Zr, Ta, Sn and Zn as a main component; A film thickness of 0.1 μm or more covering the colored film 2
A colored transparent body provided with a transparent protective film having a thickness of 00 μm or less.
【０００８】本発明において対象となる透明基板は、自
動車用窓ガラスとして使用でき、被膜硬化する加熱温度
に耐える材料であればよく、ガラス単板の他、合成樹脂
ガラス、合成樹脂や別のガラス板を積層、接着したもの
でもよく、その形態の例としては、ガラス／合成樹脂
膜、ガラス／合成樹脂膜／ガラス、ガラス／合成樹脂膜
／ガラス／合成樹脂膜、ガラス／合成樹脂膜／合成樹脂
膜、等が挙げられる。本発明において、着色膜は、該膜
を保護するためその透明基板が自動車、その他各種車
両、建造物の窓に取り付けられた時、室内側となる面に
形成されるのが好ましい。The transparent substrate to be used in the present invention may be a material that can be used as a window glass for automobiles and can withstand the heating temperature for curing the coating film. Besides the single glass plate, synthetic resin glass, synthetic resin or another glass. Plates may be laminated and adhered, and examples of forms thereof include glass / synthetic resin film, glass / synthetic resin film / glass, glass / synthetic resin film / glass / synthetic resin film, glass / synthetic resin film / synthetic Resin films and the like can be mentioned. In the present invention, the colored film is preferably formed on the surface which is the interior side when the transparent substrate is attached to the window of an automobile, other various vehicles, or a structure in order to protect the film.
【０００９】本発明において、着色膜は、スクリーン印
刷法、フレキソ印刷法、ディップ法等のいわゆる湿式法
で塗布され、後に加熱することによって硬化された膜で
ある。具体的には、Ｔｉ、Ｓｉ、Ｚｒ、Ｔａ、Ｓｎおよ
びＺｎからなる群から選ばれる少なくとも１種の金属の
酸化物を主成分とする膜中に、Ａｇ、Ａｕ、Ｃｕ、Ｐ
ｔ、Ｐｄ等の貴金属の微粒子や、Ｗの酸化物、Ｔａの酸
化物、Ｎｉの酸化物等の微粒子が分散した膜である。か
かる着色膜は、材料選択によって、熱線反射、熱線吸
収、紫外線遮蔽等の機能を有するものもある。In the present invention, the colored film is a film which is applied by a so-called wet method such as a screen printing method, a flexographic printing method, a dipping method and then cured by heating. Specifically, Ag, Au, Cu and P are contained in a film containing an oxide of at least one metal selected from the group consisting of Ti, Si, Zr, Ta, Sn and Zn as a main component.
It is a film in which fine particles of a noble metal such as t and Pd and fine particles of an oxide of W, an oxide of Ta, an oxide of Ni and the like are dispersed. Some of these colored films have functions such as heat ray reflection, heat ray absorption, and ultraviolet ray shielding, depending on the material selection.
【００１０】かかる着色膜形成用の塗布液としては、Ｔ
ｉ、Ｓｉ、Ｚｒ、Ｔａ、Ｓｎ、Ｚｎ等のアルコキシドを
含み、Ａｇ、Ａｕ、Ｃｕ、Ｐｔ、Ｐｄ等の微粒子や、Ｗ
の酸化物、Ｔａの酸化物、Ｎｉの酸化物等の微粒子が分
散した液が挙げられる。A coating solution for forming such a colored film is T
Fine particles such as Ag, Au, Cu, Pt, and Pd containing alkoxides such as i, Si, Zr, Ta, Sn, and Zn, and W
A liquid in which fine particles such as an oxide of Ta, an oxide of Ta, and an oxide of Ni are dispersed.
【００１１】本発明は、かかる着色膜を覆って、加熱に
より堅牢度、薬品耐久性が大きく向上する透明保護膜を
形成し、全被膜形成後に加熱成形或いは単なる加熱処理
をし、加熱により機械的強度、耐擦傷性、耐摩耗性、耐
候性、耐薬品性を大幅に向上させ、被膜を露出させたま
ま単板状態で使用することを可能としたことを特徴とす
るものである。According to the present invention, a transparent protective film is formed by covering the colored film, the robustness and chemical durability of which are greatly improved by heating, and after the formation of the entire film, thermoforming or simple heat treatment is performed to mechanically heat the film. It is characterized in that the strength, scratch resistance, abrasion resistance, weather resistance, and chemical resistance are significantly improved, and that it can be used in a single plate state with the coating exposed.
【００１２】かかる透明保護膜としては、スクリーン印
刷法、フレキソ印刷法、或いはディップ法等のいわゆる
湿式法で塗布され、後に加熱することによって製膜さ
れ、硬度、平滑性において優れた膜が好ましい。その材
料としては、製膜された後に残る固形部分が、ＭｇＯ、
ＳｉＯ2 、ＳｎＯ2 、Ｉｎ2 Ｏ3 、ＴｉＯ2 、ＺｎＯ、
ＷＯ3 、Ａｌ2 Ｏ3 、Ｂｉ2 Ｏ3 、ＺｒＯ2 、Ｃｒ2 Ｏ
3 、ＮｉＯ、Ｔａ2 Ｏ3、ＺｒＳｉx Ｏy 等の酸化物
や、ガラスペーストを焼成した酸化物などである材料が
挙げられる。透明保護膜用の塗布液としては、上記酸化
物の金属のアルコキシドを含む液や、上記酸化物の超微
粒子を分散した液などが挙げられる。The transparent protective film is preferably a film which is applied by a so-called wet method such as a screen printing method, a flexo printing method, or a dip method, and is then heated to form a film, which is excellent in hardness and smoothness. As the material, the solid portion remaining after the film formation is MgO,
SiO 2 , SnO 2 , In 2 O 3 , TiO 2 , ZnO,
WO 3 , Al 2 O 3 , Bi 2 O 3 , ZrO 2 , Cr 2 O
3, NiO, Ta 2 O 3 , oxides such ZrSi x O y and include material that is in an oxide obtained by firing the glass paste. Examples of the coating liquid for the transparent protective film include a liquid containing a metal alkoxide of the above oxide and a liquid in which ultrafine particles of the above oxide are dispersed.
【００１３】透明保護膜の膜厚としては、０．１μｍ
（１０００Å）未満では、耐擦傷性、耐摩耗性を十分に
改善できないことが多く、また膜厚ムラに起因する色調
ムラが発生し易いので、０．１μｍ以上が好ましい。
０．５μｍ（５０００Å）以上であると、耐久性の点で
も十分であり、干渉ムラも見えないので特に好ましい。
また、２００μｍより厚いと、加熱焼成時にクラックが
発生し易く、耐久試験でも応力により下層の着色膜と透
明保護膜との間で剥離し易いので望ましくない。また、
加熱処理時に収縮でガラスが被膜形成側に反る傾向があ
るが、膜厚が厚くなると反り量が大きくなるので、この
点からも、透明保護膜の膜厚としては、２００μｍ以下
であることが好ましい。The thickness of the transparent protective film is 0.1 μm.
If it is less than (1000Å), scratch resistance and abrasion resistance cannot be often sufficiently improved, and unevenness in color tone due to unevenness in film thickness is likely to occur, so 0.1 μm or more is preferable.
When it is 0.5 μm (5000 Å) or more, durability is sufficient and unevenness in interference is not visible, which is particularly preferable.
On the other hand, if it is thicker than 200 μm, cracks are likely to occur at the time of heating and baking, and peeling is easily caused between the lower colored film and the transparent protective film due to stress even in the durability test, which is not desirable. Also,
Although the glass tends to warp toward the film formation side due to shrinkage during heat treatment, the amount of warpage increases as the film thickness increases. From this point as well, the film thickness of the transparent protective film may be 200 μm or less. preferable.
【００１４】本発明の着色透明体の、上記被膜が形成さ
れた部分の可視光線透過率は任意に設定できるが、プラ
イバシーガラスとして可視域低透過を目的とする場合、
可視光線透過率は７０％以下、特に５５％以下が望まし
い。本発明の着色透明体は、上記の着色膜および透明保
護膜の他に、さらに、周辺部遮光層や、防曇用通電プリ
ントが設けられていてもよい。The visible light transmittance of the portion of the colored transparent body of the present invention on which the above-mentioned coating is formed can be arbitrarily set, but in the case of low transparency in the visible region as privacy glass,
The visible light transmittance is preferably 70% or less, particularly 55% or less. The colored transparent body of the present invention may be further provided with a peripheral light shielding layer and an anti-fog energization print in addition to the colored film and the transparent protective film.
【００１５】本発明の着色透明体の一連の製造方法を、
透明基板としてガラス板を用いる場合を例にして以下に
説明する。まず、所望の形状に切断されたガラス板を用
意する。合わせガラスとして用いる場合には二枚のガラ
ス板を合わせガラス用素板ガラスとして用意する。この
ガラスの被膜をコートする面を十分に酸化セリウムの粉
末を研磨材として用いながら洗浄し、純水リンス、乾
燥、除塵する。A series of production methods of the colored transparent body of the present invention are described below.
The case where a glass plate is used as the transparent substrate will be described below as an example. First, a glass plate cut into a desired shape is prepared. When it is used as a laminated glass, two glass plates are prepared as a glass sheet for laminated glass. The surface of the glass to be coated with the glass is washed while sufficiently using cerium oxide powder as an abrasive, rinsed with pure water, dried and dust-removed.
【００１６】次に、スクリーン印刷法、フレキソ印刷
法、スプレー法、ディッピング塗布法、ＣＶＤ法、ＣＬ
Ｄ法、メッキ法、印刷法等の湿式法を用いて、着色膜用
の塗布液を塗布し、仮焼成という８０℃〜１５０℃のオ
ーブンで約５〜３０分乾燥させる処理工程を通し、膜中
の有機溶媒を蒸発、乾燥硬化させる。こうして着色膜を
設けた後、次に被膜面に、スクリーン印刷法、フレキソ
印刷法、スプレー法、ディッピング塗布法、ＣＶＤ法、
ＣＬＤ法、メッキ法、印刷法等の湿式法を用いて、透明
保護膜用の塗布液またはガラスフリットペーストを、厚
さ最低０．０６μｍ〜最大４００μｍで塗布する。Next, screen printing method, flexographic printing method, spraying method, dipping coating method, CVD method, CL
The coating solution for the colored film is applied by a wet method such as D method, plating method, or printing method, and the film is passed through a treatment step of calcination that is dried in an oven at 80 ° C. to 150 ° C. for about 5 to 30 minutes. The organic solvent therein is evaporated, dried and cured. After providing the colored film in this manner, the screen surface is then subjected to screen printing, flexographic printing, spraying, dipping coating, CVD,
A wet coating method such as a CLD method, a plating method, or a printing method is used to apply a coating solution for a transparent protective film or a glass frit paste to a thickness of at least 0.06 μm to a maximum of 400 μm.
【００１７】その後、仮焼成という８０℃〜１５０℃の
オーブンで約５〜３０分乾燥させる処理工程を通し、最
上層に含まれる有機溶媒を十分蒸発、乾燥硬化させ、そ
の後の短期間の保管、ある程度の被膜面の機械接触には
耐える状態にする。しかし、上述の状態では最外層被膜
はまだ十分硬質でなく、また有機溶媒が蒸発した被膜は
微視的にはポーラスであり、十分な耐久性は持たない。
上記透明保護膜の組成によっては、仮焼成にはＵＶ照射
を併用、或いは単独で用いることでその効果が得られる
こともある。After that, the organic solvent contained in the uppermost layer is sufficiently evaporated and dried and cured through a treatment step of calcination in an oven at 80 ° C. to 150 ° C. for about 5 to 30 minutes, followed by short-term storage, The machine should be able to withstand some mechanical contact with the coating surface. However, in the above-mentioned state, the outermost layer coating is not yet sufficiently hard, and the coating obtained by evaporation of the organic solvent is microscopically porous and does not have sufficient durability.
Depending on the composition of the transparent protective film, the effect may be obtained by using UV irradiation together or alone for the calcination.
【００１８】その後、ガラス成形炉で５８０〜６８０℃
のガラス成形温度まで加熱し、ガラス自重曲げ方法、或
いはプレス曲げ方法等の成型方法で曲げ成形を行う。透
明保護膜はこの加熱時に、およそ１／２に収縮し密度を
増し、ポーラスでない強固な膜になるが、ガラス軟化温
度で収縮が起こるとガラスが反り易いので、ガラス軟化
点温度より低温に被膜が焼きつけられる温度が有り、ガ
ラス軟化時には既に十分収縮硬化している材料、組成を
選ぶのが都合がよい。After that, in a glass forming furnace at 580 to 680 ° C.
Then, the glass is heated to the glass forming temperature and the bending is performed by a glass weight bending method or a press bending method. When heated, the transparent protective film shrinks to about 1/2 and increases in density to become a non-porous, strong film, but when shrinkage occurs at the glass softening temperature, the glass tends to warp, so the film is coated at a temperature lower than the glass softening temperature. It is convenient to select a material and composition that have a baking temperature and are already sufficiently shrink-hardened when the glass softens.
【００１９】透明保護膜収縮時に被膜にクラックが入る
ことがあるので、組成の選択には熟慮が必要である。必
要に応じて、成形直後の急冷で強化ガラスにする。透明
保護膜の組成によってはガラス成形後に保護被膜を設
け、ガラスが変形しない５００℃以下の温度で硬化する
こともあり得る。Since the film may crack when the transparent protective film shrinks, careful consideration must be taken in selecting the composition. If necessary, tempered glass is formed by quenching immediately after molding. Depending on the composition of the transparent protective film, a protective coating may be provided after the glass is molded, and the glass may be cured at a temperature of 500 ° C. or lower at which the glass is not deformed.
【００２０】[0020]
［実施例１］酸化セリウム粉で洗浄した後、純水でリン
ス、乾燥させたソーダライムガラスの片面に、フレキソ
印刷法によってＴｉ−Ｓｉのアルコキシドを含みびＡｕ
微粒子が分散した塗布液を厚さ４００±５０Åの厚さで
塗布し、１２０℃のオーブンで１０分間仮焼成し、着色
膜を形成した。次に、スクリーン印刷法で、ＳｉＯ2 −
ＰｂＯ−Ｂ2 Ｏ3 系の鉛ガラスペーストを厚さ２０μｍ
の膜厚で塗布し、８０℃オーブンで２０分間仮焼成し、
透明保護膜を形成した。[Example 1] After cleaning with cerium oxide powder, rinsed with pure water and dried on one surface of a soda lime glass containing a Ti-Si alkoxide by a flexographic printing method and containing Au.
The coating liquid in which the fine particles were dispersed was applied in a thickness of 400 ± 50Å and calcinated in an oven at 120 ° C. for 10 minutes to form a colored film. Next, by a screen printing method, SiO 2 −
PbO-B 2 O 3 based lead glass paste with a thickness of 20 μm
Coating with the film thickness of
A transparent protective film was formed.
【００２１】その後、ガラスのプレス成形炉で６８０℃
まで昇温し、プレスで曲げ成形した。曲げ成形時に、空
気吹き付けで急速冷却することにより強化ガラスにし
た。透明保護膜の膜厚は１０μｍであった。このように
して製造された窓ガラスの性能は表１のようになった。Then, in a glass press molding furnace, 680 ° C.
The temperature was raised to, and bending was performed by pressing. At the time of bending, it was made into tempered glass by rapidly cooling by blowing air. The film thickness of the transparent protective film was 10 μm. The performance of the window glass thus manufactured is shown in Table 1.
【００２２】[0022]
【表１】 [Table 1]
【００２３】このようにして製造されたガラスと、透明
保護膜を設けなかったガラスについて、自動車用窓ガラ
スの通常の品質評価方法で評価した結果を表２に示す。Table 2 shows the results of the evaluation of the glass thus manufactured and the glass not provided with the transparent protective film by the usual quality evaluation method for automobile window glass.
【００２４】[0024]
【表２】 [Table 2]
【００２５】この結果より、透明保護膜を設けることに
因って耐擦傷性等の耐久性が大幅に改善できたことがわ
かる。また、透明保護膜形成時の溶媒の濃度を調整し
て、加熱成形後の透明保護膜の膜厚を変えた場合の耐擦
傷性、耐摩耗性について評価した結果を表３に示す。From these results, it can be seen that the provision of the transparent protective film significantly improved the durability such as scratch resistance. Table 3 shows the results of evaluation of scratch resistance and abrasion resistance when the concentration of the solvent during the formation of the transparent protective film was adjusted and the film thickness of the transparent protective film after heat molding was changed.
【００２６】[0026]
【表３】 [Table 3]
【００２７】この結果より、透明保護膜の厚さが０．１
μｍ以上で耐摩耗性、耐擦傷性が改善できたことがわか
る。From this result, the thickness of the transparent protective film was 0.1.
It can be seen that the wear resistance and the scratch resistance were improved when the thickness was at least μm.
【００２８】［実施例２］板厚３. ５ｍｍのブロンズガ
ラスを自動車バックライト窓ガラスの形状に切断した。
このガラスの被膜をコートする面を十分に酸化セリウム
の粉末を研磨材として用いながら洗浄し、純水リンス、
乾燥、除塵した。次にフレキソ印刷法によってＴｉ−Ｓ
ｉのアルコキシドを含み、Ｃｕの微粒子が分散した塗布
液を厚さ４００±５０Åの厚さで塗布し、１２０℃のオ
ーブンで１０分間仮焼成した。[Example 2] Bronze glass having a plate thickness of 3.5 mm was cut into a shape of an automobile backlight window glass.
The surface to be coated with this glass film is thoroughly washed using cerium oxide powder as an abrasive, and rinsed with pure water,
Dried and dust removed. Next, the Ti-S
A coating solution containing the alkoxide of i and having Cu fine particles dispersed therein was applied in a thickness of 400 ± 50Å, and pre-baked in an oven at 120 ° C. for 10 minutes.
【００２９】次に、ナイロン＃５０番の目粗さのスクリ
ーン印刷法で、Ｓｉ−Ｔｉ（原子比50：50）のアルコキ
シドを含む塗布液を１μｍの膜厚で塗布し、１２０℃の
オーブンで１０分間加熱し、塗布被膜を乾燥させた。そ
の後、ガラスのプレス成形炉で６８０℃まで昇温し、プ
レスで所定の形状に曲げ成形した。曲げ成形時に、空気
吹き付けで急速冷却することによって強化ガラスにし
た。こうして製造された窓ガラスの性能は表４および表
５のようになり、自動車用窓ガラスとして単板で使用し
ても差し支えないことが確認できた。また、透明保護膜
の膜厚は、０．５μｍであった。Next, a coating solution containing an alkoxide of Si--Ti (atomic ratio 50:50) was applied in a thickness of 1 .mu.m by a screen printing method with nylon # 50 roughness, and the coating solution was heated in an oven at 120.degree. The coated film was dried by heating for 10 minutes. Then, the temperature was raised to 680 ° C. in a glass press molding furnace, and the glass was bent into a predetermined shape by pressing. During bending, the glass was tempered by rapid cooling by blowing air. The performance of the window glass thus manufactured is as shown in Tables 4 and 5, and it was confirmed that the window glass for automobiles can be used as a single plate as a single plate. The film thickness of the transparent protective film was 0.5 μm.
【００３０】[0030]
【表４】 [Table 4]
【００３１】[0031]
【表５】 [Table 5]
【００３２】［実施例３］板厚３. ５ｍｍのブロンズガ
ラスを自動車バックライト窓ガラスの形状に切断した。
このガラスの被膜をコートする面を十分に酸化セリウム
の粉末を研磨材として用いながら洗浄し、純水リンス、
乾燥、除塵した。次にフレキソ印刷法によってＴｉ−Ｓ
ｉのアルコキシドを含み、Ｐｔが分散した塗布液を厚さ
４００±５０Åの厚さで塗布し、１２０℃のオーブンで
１０分間仮焼成した。Example 3 Bronze glass having a plate thickness of 3.5 mm was cut into the shape of an automobile backlight window glass.
The surface to be coated with this glass film is thoroughly washed using cerium oxide powder as an abrasive, and rinsed with pure water,
Dried and dust removed. Next, the Ti-S
A coating solution containing the alkoxide of i and having Pt dispersed therein was applied to a thickness of 400 ± 50Å, and pre-baked in an oven at 120 ° C. for 10 minutes.
【００３３】次に、スクリーン印刷法で、ＳｉＯ2 −Ｐ
ｂＯ−Ｂ2 Ｏ3 系の鉛ガラスペーストを厚さ２０μｍの
膜厚で塗布成膜成形し、８０℃オーブンで２０分間仮焼
成した。その後、ガラスのプレス成形炉で６８０℃まで
昇温し、プレスで所定の形状に曲げ成形した。曲げ成形
時に、空気吹き付けで急速冷却することによって強化ガ
ラスにした。こうして製造された窓ガラスの性能は表６
および表７のようになり、自動車用窓ガラスとして単板
で使用しても差し支えないことが確認できた。また、透
明保護膜の膜厚は１０μｍであった。Next, by a screen printing method, SiO 2 -P
A bO—B 2 O 3 based lead glass paste was applied and formed into a film having a thickness of 20 μm, and prebaked in an oven at 80 ° C. for 20 minutes. Then, the temperature was raised to 680 ° C. in a glass press molding furnace, and the glass was bent into a predetermined shape by pressing. During bending, the glass was tempered by rapid cooling by blowing air. The performance of the window glass manufactured in this way is shown in Table 6.
And, as shown in Table 7, it has been confirmed that it can be used as a single plate as an automobile window glass. The film thickness of the transparent protective film was 10 μm.
【００３４】[0034]
【表６】 [Table 6]
【００３５】[0035]
【表７】 [Table 7]
【００３６】[0036]
【発明の効果】本発明を用いれば、機械的強度、耐擦傷
性、耐摩耗性、耐候性、耐薬品性が大幅に向上し、被膜
を露出させたまま単板状態で使用することが可能な着色
透明体を提供することが可能となる。本発明の着色透明
体は、自動車、鉄道車両、航空機などの窓に好適に使用
できる。Industrial Applicability According to the present invention, the mechanical strength, scratch resistance, abrasion resistance, weather resistance and chemical resistance are greatly improved, and it is possible to use it as a single plate with the coating exposed. It is possible to provide a colored transparent body. The colored transparent body of the present invention can be suitably used for windows of automobiles, railway vehicles, airplanes and the like.
Claims (2)
ＳｎおよびＺｎからなる群から選ばれる少なくとも１種
の金属の酸化物を主成分とする膜中に、金属および／ま
たは金属酸化物の微粒子が分散した着色膜と、該着色膜
を覆って膜厚０．１μｍ以上２００μｍ以下の透明保護
膜とが設けられた着色透明体。1. A transparent substrate on which Ti, Si, Zr, Ta,
A colored film in which fine particles of a metal and / or a metal oxide are dispersed in a film containing an oxide of at least one metal selected from the group consisting of Sn and Zn as a main component, and a film thickness covering the colored film. A colored transparent body provided with a transparent protective film having a thickness of 0.1 μm or more and 200 μm or less.
びＰｄからなる群から選ばれる少なくとも１種であり、
前記金属酸化物は、Ｗ、ＴａおよびＮｉからなる群から
選ばれる少なくとも１種の金属の酸化物であることを特
徴とする請求項１の着色透明体。2. The metal is at least one selected from the group consisting of Ag, Au, Cu, Pt and Pd,
The colored transparent body according to claim 1, wherein the metal oxide is an oxide of at least one metal selected from the group consisting of W, Ta, and Ni.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11915494A JPH07330379A (en) | 1994-05-31 | 1994-05-31 | Colored transparent material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11915494A JPH07330379A (en) | 1994-05-31 | 1994-05-31 | Colored transparent material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07330379A true JPH07330379A (en) | 1995-12-19 |
Family
ID=14754264
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11915494A Pending JPH07330379A (en) | 1994-05-31 | 1994-05-31 | Colored transparent material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07330379A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997031871A1 (en) * | 1996-02-27 | 1997-09-04 | Nippon Sheet Glass Co., Ltd. | Glass article covered with colored film |
| EP0811583A1 (en) * | 1995-12-26 | 1997-12-10 | Nippon Sheet Glass Co., Ltd. | Glass article covered with ultraviolet-absorbing colored coat |
| EP0820966A1 (en) * | 1996-07-23 | 1998-01-28 | Nippon Sheet Glass Co. Ltd. | Colored film-coated glass article |
| JPH10203848A (en) * | 1997-01-20 | 1998-08-04 | Toshiba Glass Co Ltd | Colored glass |
| JP2000351917A (en) * | 1999-06-09 | 2000-12-19 | Asahi Glass Co Ltd | Coating liquid for forming oxide membrane, formation of oxide membrane and substrate with oxide membrane |
| US6515631B1 (en) | 1999-08-17 | 2003-02-04 | Central Glass Company, Limited | Glass pane with functional film and process producing same |
| WO2021002304A1 (en) * | 2019-07-01 | 2021-01-07 | 日本電気硝子株式会社 | Film-covered transparent base plate and top plate for cooking device |
| WO2023120047A1 (en) * | 2021-12-21 | 2023-06-29 | 日本電気硝子株式会社 | Film-attached transparent substrate, top plate for cooker, window glass for heat cooker, and cover glass |
-
1994
- 1994-05-31 JP JP11915494A patent/JPH07330379A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0811583A1 (en) * | 1995-12-26 | 1997-12-10 | Nippon Sheet Glass Co., Ltd. | Glass article covered with ultraviolet-absorbing colored coat |
| EP0811583A4 (en) * | 1995-12-26 | 1998-06-10 | Nippon Sheet Glass Co Ltd | Glass article covered with ultraviolet-absorbing colored coat |
| WO1997031871A1 (en) * | 1996-02-27 | 1997-09-04 | Nippon Sheet Glass Co., Ltd. | Glass article covered with colored film |
| EP0820966A1 (en) * | 1996-07-23 | 1998-01-28 | Nippon Sheet Glass Co. Ltd. | Colored film-coated glass article |
| JPH10203848A (en) * | 1997-01-20 | 1998-08-04 | Toshiba Glass Co Ltd | Colored glass |
| JP2000351917A (en) * | 1999-06-09 | 2000-12-19 | Asahi Glass Co Ltd | Coating liquid for forming oxide membrane, formation of oxide membrane and substrate with oxide membrane |
| US6515631B1 (en) | 1999-08-17 | 2003-02-04 | Central Glass Company, Limited | Glass pane with functional film and process producing same |
| WO2021002304A1 (en) * | 2019-07-01 | 2021-01-07 | 日本電気硝子株式会社 | Film-covered transparent base plate and top plate for cooking device |
| WO2023120047A1 (en) * | 2021-12-21 | 2023-06-29 | 日本電気硝子株式会社 | Film-attached transparent substrate, top plate for cooker, window glass for heat cooker, and cover glass |
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