JPH04193744A - High heat-resistant colorless ultraviolet cutting film and transparent glass having this coated film - Google Patents
High heat-resistant colorless ultraviolet cutting film and transparent glass having this coated filmInfo
- Publication number
- JPH04193744A JPH04193744A JP32104890A JP32104890A JPH04193744A JP H04193744 A JPH04193744 A JP H04193744A JP 32104890 A JP32104890 A JP 32104890A JP 32104890 A JP32104890 A JP 32104890A JP H04193744 A JPH04193744 A JP H04193744A
- Authority
- JP
- Japan
- Prior art keywords
- film
- cerium
- titanium
- high heat
- ultraviolet
- 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
- 239000011521 glass Substances 0.000 title claims abstract description 10
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 13
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000010936 titanium Substances 0.000 claims abstract description 12
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 11
- 238000000576 coating method Methods 0.000 claims abstract description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000000758 substrate Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 13
- 238000010304 firing Methods 0.000 claims description 12
- 150000002902 organometallic compounds Chemical class 0.000 claims description 6
- 230000000903 blocking effect Effects 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 abstract description 5
- 239000011259 mixed solution Substances 0.000 abstract description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 238000007496 glass forming Methods 0.000 abstract 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 14
- 238000002834 transmittance Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 6
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- 238000000411 transmission spectrum Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- TZIBOXWEBBRIBM-UHFFFAOYSA-N cerium(3+) oxygen(2-) titanium(4+) Chemical compound [O--].[O--].[Ti+4].[Ce+3] TZIBOXWEBBRIBM-UHFFFAOYSA-N 0.000 description 1
- GGVUYAXGAOIFIC-UHFFFAOYSA-K cerium(3+);2-ethylhexanoate Chemical compound [Ce+3].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O GGVUYAXGAOIFIC-UHFFFAOYSA-K 0.000 description 1
- JITPFBSJZPOLGT-UHFFFAOYSA-N cerium(3+);propan-2-olate Chemical compound [Ce+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] JITPFBSJZPOLGT-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 150000003278 haem Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- KBHBDZQAQRNXRB-UHFFFAOYSA-N propan-2-olate;titanium(3+) Chemical compound [Ti+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] KBHBDZQAQRNXRB-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- -1 titanium organometallic compound Chemical class 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Surface Treatment Of Glass (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、照明ランプ用ガラス等、高温環境下で使用さ
れる透明ガラスに使用するための高耐熱性無色紫外線カ
ット膜に関する。また、本発明は、上記の被膜を備えた
紫外線カッ１〜ガラスに関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a highly heat-resistant colorless ultraviolet ray cutting film for use in transparent glass used in high-temperature environments, such as glass for lighting lamps. The present invention also relates to an ultraviolet glass provided with the above coating.
可視透過率の大きな、すなわち無色透明な紫外線カット
膜としては、従来、ＺｎＯ等が使われている。また、Ｔ
ｌＯ２からなる紫外線吸収膜も既知である。しかし、Ｚ
ｎＯはその成膜性の点から５ＩＯ２をバインダーとして
用い、その混合物として成膜されることが多い。このた
め、５００〜６００°Ｃ以」二の温度ではＺｎがＳｉＯ
□中に拡散することにより結晶が壊れ紫外線吸収能が失
われる。また、Ｔ」０２は、高温環境下での使用によっ
て、結晶粒の成長が起こるため、膜全体に白濁が生じて
透明性が失われる。このため、使用時に７００°Ｃ程度
まで温度が−１−ＩＩする照明ランプ等については、こ
れらのガラス膜を使用することができなかった。一方、
多層膜中の高屈折率膜としてはＴｌＯ２やＴａ、 Ｏ６
等が使用されているか、通常、屈折率は２．２〜２．３
程度である。多層膜は、高屈折率膜と低屈折率膜の交互
積層構造であり、高屈折率膜の屈折率が高い程、その性
能および安定性か高い。屈折率を高めるために焼成温度
を高め、あるいは焼成後高温で高屈折率化処理を行なう
方法も提案されているか、この場合、やはり、結晶粒の
成長か起こり、透明性か損なわれるという問題かあった
。このため、高温時にも透明性を失わない紫外線カッ［
〜１模および高屈折率セラミック膜か求められていた。Conventionally, ZnO or the like has been used as a colorless and transparent ultraviolet ray cutting film with a high visible transmittance. Also, T
Ultraviolet absorbing films made of lO2 are also known. However, Z
In view of its film-forming properties, nO is often formed into a film using 5IO2 as a binder and as a mixture thereof. Therefore, at temperatures above 500 to 600°C, Zn becomes SiO
□ Diffusion into the interior causes the crystal to break and lose its ultraviolet absorption ability. Furthermore, when T'02 is used in a high-temperature environment, crystal grains grow, so the entire film becomes cloudy and loses its transparency. For this reason, these glass films could not be used for lighting lamps and the like whose temperature reaches -1-II up to about 700°C during use. on the other hand,
High refractive index films in the multilayer film include TlO2, Ta, and O6.
Usually, the refractive index is 2.2 to 2.3.
That's about it. A multilayer film has a structure in which high refractive index films and low refractive index films are alternately laminated, and the higher the refractive index of the high refractive index film, the higher its performance and stability. Have any methods been proposed to increase the firing temperature to increase the refractive index, or to perform high refractive index treatment at high temperatures after firing? In this case, would the problem still be that crystal grain growth would occur and transparency would be impaired? there were. For this reason, it has UV protection that does not lose its transparency even at high temperatures.
~1 model and high refractive index ceramic films were sought.
本発明者は、従来、黄色着色被膜として知られていたＣ
ｅＯ２−ＴｊＯ２系セラミック膜に着］」シた。The present inventor discovered that C, which was conventionally known as a yellow colored film,
eO2-TjO2-based ceramic membrane].
ＣｅＯ，−１］０．、系セラミック膜は、熱線反射ガラ
スとして（特開昭５４−１０１８２１号）あるいは固体
表面への七色剤として（特開昭６１−３４１８５号、６
３−１０３０８３号）、その利用か提案されているが、
いずれもセリウム酸化物が黄色であることを利用したも
のてル）って、紫外線カッ１−膜としての利用は特に提
案されていなかった。木発明者は、ＣｅＯ２−Ｔｉｅ２
系セラミック膜において、ＣｅＯ２含有量を対１１０２
重量比で４．５以下に抑えることにより、］」０．の結
晶粒の成長が顕著に抑制され、高温環境下でも白濁を生
しないこと、しかも、該膜は紫外線吸収性に優れている
こと、さらに、高温焼成によっても透明性か損なわれな
いため高屈折率膜の形成か容易であるという予想外の事
実を見出した。CeO,-1]0. , ceramic films have been used as heat-reflecting glass (Japanese Patent Application Laid-Open No. 54-101821) or as a seven-color agent on solid surfaces (Japanese Patent Application Laid-Open No. 61-34185, 6).
3-103083), its use has been proposed,
None of these methods took advantage of the yellow color of cerium oxide; however, no particular proposal had been made for its use as an ultraviolet ray-protecting film. The tree inventor is CeO2-Tie2
In the system ceramic film, the CeO2 content is 1102
By suppressing the weight ratio to 4.5 or less, ]'0. The growth of crystal grains in the film is significantly suppressed, and it does not become cloudy even in high-temperature environments.Moreover, the film has excellent ultraviolet absorption properties, and also has a high refractive index because its transparency is not impaired even by high-temperature firing. We discovered an unexpected fact that it is easy to form a film with high efficiency.
本発明によれば、チタンおよびセリウムの各有機金属化
合物を、チタンとセリウムの重量比がそれぞれの酸化物
換算で］ ： ０．０２〜Ｉ ： ４．５であるように
有機溶媒に混合し、該混合液を暴扱に塗布し、４００〜
１０００°Ｃて焼成することにより得られる高ｌｔ１熱
性無色紫外線カッ１〜膜か提供される。According to the present invention, each organometallic compound of titanium and cerium is mixed in an organic solvent such that the weight ratio of titanium to cerium is 0.02 to 4.5 in terms of the respective oxides, The mixed solution was applied with rough treatment, and 400~
A high lt1 thermal colorless ultraviolet light film obtained by firing at 1000°C is provided.
さらに、本発明によれば、−Ｉ−記被膜を有する透明カ
ラスか提供される。Furthermore, according to the present invention, there is provided a transparent glass having a coating described in -I-.
本発明において、チタン、セリウムの有機金属化合物と
しては、金属アルコキシ１−を好適に用いることができ
る。具体的には、チタニウムテ１−ライソプロポキシド
、セリウムトリイソプロポキシ−；３−
１−か挙げられる。また、その他の有機金属化合物どし
てカルボン酸塩やβ−ジケトン錯体等が用いられる。In the present invention, metal alkoxy 1- can be suitably used as the organometallic compound of titanium and cerium. Specific examples include titanium triisopropoxide and cerium triisopropoxy;3-1-. Other organometallic compounds such as carboxylic acid salts and β-diketone complexes are also used.
上記有機金属化合物な溶解する有機溶媒としては、アル
コール類、ケ１−ン酸煩、β−ジケｌ−ン煩等の一般的
な有機溶媒を用いることかできる。As the organic solvent in which the above-mentioned organometallic compound is dissolved, general organic solvents such as alcohols, carbonate, β-dicarbonate, and the like can be used.
本発明の組成物を製造するための混合方法は限定されな
い。これを基板−１−に塗布する方法としては、ティッ
プ法、スピンコード法等、既知の方法を適宜用いること
ができる。膜厚および加熱方法は必要に応して適当な方
法を用いることができる。The mixing method for producing the composition of the present invention is not limited. As a method for applying this to the substrate-1-, known methods such as a tip method and a spin code method can be used as appropriate. For the film thickness and heating method, an appropriate method can be used as necessary.
組成物におけるセリウム／チタン含有量比は、酸化物換
算値で０．０２〜４．５とする。０．０２未満であると
結晶粒成長を抑制する効果がない。４，５を超えると黄
色性が強くなり無色性が損なわれる。The cerium/titanium content ratio in the composition is 0.02 to 4.5 in terms of oxide. If it is less than 0.02, there is no effect of suppressing grain growth. If it exceeds 4.5, yellowness becomes strong and colorlessness is impaired.
本発明にしたがって無色紫外線カット膜を形成するには
、規定の混合比のセリウｔｚ／チタン有機金属化合物混
合溶液を法盤七に塗付し、これを加熱して該イ１機金属
化合物を分解させ酸化チタン−酸化セリウム膜を形成し
た後で４００〜１０００°Ｃの加熱処理を施してもよい
し、組成物を基板上に塗布した後、４００〜１０００°
Ｃて加熱分解と焼成を同時に行なってもよい。焼成温度
か４００°Ｃ未満であると有機金属化合物の分解反応が
充分に進行しない。高屈折率の膜とするためには焼成温
度を８００°Ｃ以上とする。１０００°Ｃを超えて焼成
を行なっても屈折率はそれ以下の場合に比Ｉ咬して有彦
、には改善されない。In order to form a colorless ultraviolet ray blocking film according to the present invention, a mixed solution of Cerium tz/titanium organometallic compound at a specified mixing ratio is applied to the base plate 7, and this is heated to decompose the metal compound. After forming the titanium oxide-cerium oxide film, heat treatment may be performed at 400 to 1000°C, or after coating the composition on the substrate, heat treatment may be performed at 400 to 1000°C.
Thermal decomposition and calcination may be performed simultaneously. If the firing temperature is less than 400°C, the decomposition reaction of the organometallic compound will not proceed sufficiently. In order to obtain a film with a high refractive index, the firing temperature is set to 800°C or higher. Even if firing is carried out at a temperature exceeding 1000°C, the refractive index is not improved to the extent that it is compared to that at temperatures lower than 1000°C.
〔発明の効果〕
本発明の紫外線カッ１〜膜は、高温環境下でも白濁を生
しることがないので、幅広い温度範囲にわたって透明性
を損なわずに使用することができる。[Effects of the Invention] The ultraviolet light coating of the present invention does not become cloudy even in high-temperature environments, so it can be used over a wide temperature range without impairing transparency.
また、高温処理によって高屈折率化が達成できるので低
屈折率膜と組合せて反射率の大きな多層膜の形成に使用
することができる。また、本発明の高屈折率膜は屈折率
が高いので、低屈折率膜との交互積層単位の数が少なく
て済み、多層膜全体としての熱的・機械的安定性か高く
なる。さらに、本発明による紫外線カット膜は無色性に
優れている。このため、本発明の紫外線カッｌ−膜およ
びガラスは、車両や船舶等の照明ランプを製造する場合
に特に好適である。Further, since a high refractive index can be achieved by high temperature treatment, it can be used in combination with a low refractive index film to form a multilayer film with a high reflectance. Furthermore, since the high refractive index film of the present invention has a high refractive index, the number of alternately laminated units with low refractive index films is small, and the thermal and mechanical stability of the multilayer film as a whole is increased. Furthermore, the ultraviolet cut film according to the present invention is excellent in colorlessness. Therefore, the ultraviolet ray-coating film and glass of the present invention are particularly suitable for manufacturing lighting lamps for vehicles, ships, and the like.
尖息孤よ
チタニウムテトライソプロポキシドとセリウムトリイソ
プロシトを、酸化チタンと酸化セリウムが重量比で１：
０．１２となるように２−メトキシエタノールに溶解し
、還流して均一とした後、２−メトキシエタノールで重
量調整を行ない、酸化物換算で１０％の塗布液を得た。Titanium tetraisopropoxide and cerium triisopropoxide, titanium oxide and cerium oxide in a weight ratio of 1:
After dissolving in 2-methoxyethanol to give a concentration of 0.12% and refluxing to make it uniform, the weight was adjusted with 2-methoxyethanol to obtain a coating solution with a concentration of 10% in terms of oxide.
石英ガラス上にこの塗布液をデイツプ法で塗布し、６０
０°Ｃで１０分焼成して透明な紫外線カット膜を得た。This coating solution was applied onto quartz glass using the dip method, and
A transparent ultraviolet cut film was obtained by baking at 0°C for 10 minutes.
第１図にその吸収特性を示す。Figure 1 shows its absorption characteristics.
この膜をさらに１０００℃で３０分焼成して、屈折率が
２．７の透明膜を得た。This film was further baked at 1000° C. for 30 minutes to obtain a transparent film with a refractive index of 2.7.
去遣１殴
チタニウムテトライソプロポキシドと２−エチルヘキサ
ン酸セリウムを、酸化チタンと酸化セリウムが重量比で
１ ： ０．４となるようにイソプロピルアルコールと
１−ルエン１：１混合液に溶解し、均一に攪拌した後、
イソプロピルアルコールとトルエン１：１混合液で重量
調整を行ない、酸化物換算で１０％の塗布液を得た。石
英ガラス上にこの塗布液をデイツプ法で塗布し、６００
℃で１０分焼成して透明な紫外線カット膜を得た。第２
図にその吸収特性を示す。Dissolve titanium tetraisopropoxide and cerium 2-ethylhexanoate in a 1:1 mixture of isopropyl alcohol and 1-toluene so that the weight ratio of titanium oxide and cerium oxide is 1:0.4. , after stirring evenly,
The weight was adjusted with a 1:1 mixture of isopropyl alcohol and toluene to obtain a coating solution with a concentration of 10% in terms of oxides. This coating solution was applied onto quartz glass using the dip method, and
A transparent ultraviolet cut film was obtained by baking at ℃ for 10 minutes. Second
The figure shows its absorption characteristics.
この膜をさらに１０００℃で３０分焼成して、屈折率が
２．７の透明膜を得た。This film was further baked at 1000° C. for 30 minutes to obtain a transparent film with a refractive index of 2.7.
迄較析よ
チタニウムテトライソプロポキシドのみを用いた他は実
施例１と同様にして、石英ガラス上にＴｊＯ□膜を形成
した。この膜を１０００℃で３０分焼成したところ、膜
中の結晶粒成長により白濁が生じ、透過率の非常に低い
膜となった。Calibration Analysis A TjO□ film was formed on quartz glass in the same manner as in Example 1 except that only titanium tetraisopropoxide was used. When this film was baked at 1000° C. for 30 minutes, clouding occurred due to the growth of crystal grains in the film, resulting in a film with very low transmittance.
３〜４、比・ ２〜４
ＣｅＯ□とＴｉＯ２、ｚｒＯ□およびＴａ２０５とのそ
れぞれの混合酸化物からなる膜を上記の例と同様な方法
によって形成した。また、同様にＴｉＯ２だけからなる
膜を形成した。これらの膜の組成を第１表に、透過スペ
クトルを第３図に示す（比較例５のみ第４図に示す）。3-4, ratio 2-4 Films made of mixed oxides of CeO□, TiO2, zrO□ and Ta205 were formed in the same manner as in the above example. Similarly, a film made only of TiO2 was formed. The compositions of these films are shown in Table 1, and the transmission spectra are shown in FIG. 3 (only Comparative Example 5 is shown in FIG. 4).
比較例２Ｔ１ｏ２
比較例４ ＺｒＯ２： Ｃｅ０２＝１ ：
０．５比較例５ Ｔ、ａ２０ｓ ： Ｃｅ０
２＝ １ ： ０．５本発明の紫外線カット膜は従来の
組成の紫外線カット膜と比較して紫外線透過率が非常に
低いことがわかる。Comparative example 2 T1o2 Comparative example 4 ZrO2: Ce02=1:
0.5 Comparative Example 5 T, a20s: Ce0
2=1:0.5 It can be seen that the ultraviolet cut film of the present invention has a very low ultraviolet transmittance compared to the ultraviolet cut film of the conventional composition.
一！１５、比較例５
本発明によるｃｅｏ２含有膜の紫外線吸収性をさらに厳
密に示すため、ＴｉＯ２とＣｅＯ２の重量比が１＝４の
膜の上にさらに５ｊｏ２を被覆し、表面反射による透過
率の低下を除いた上で透過スペクトルを測定した（実施
例５）。また、ＴｉＯ２膜の上に同様に５１ｏ２を用い
て無反射設計を行なった膜についても透過スペクトルを
測定した（比較例５）。結果を第４図に示す。one! 15. Comparative Example 5 In order to more precisely demonstrate the ultraviolet absorbability of the ceo2-containing film according to the present invention, 5jo2 was further coated on a film with a weight ratio of TiO2 and CeO2 of 1=4 to reduce the transmittance due to surface reflection. The transmission spectrum was measured after removing (Example 5). In addition, the transmission spectrum was also measured for a film in which 51o2 was similarly used on the TiO2 film to perform a non-reflection design (Comparative Example 5). The results are shown in Figure 4.
本発明の紫外線カット膜は従来の組成の紫外線−８＝
カット膜と比較して紫外線吸収能が非常に大きいことが
わかる。It can be seen that the ultraviolet ray cutting film of the present invention has a much higher ultraviolet absorption ability than the ultraviolet ray -8= cutting film having a conventional composition.
扁−温」１別」４」−る−透過−皐−二−屈−低率変化
ＴｌＯ２：ＣｅＯ２の組成比が０．１２．０．４および
２である本発明による紫外線カッ１〜膜ならびにＴｉＯ
２のみからなる膜を作成し、それぞれ５００°Ｃ１７０
０℃、８００℃、９００℃および１０００℃で焼成した
後、透過スペクトルを測定し、可視透過率に求めた。５
００℃焼成時の可視透過率を１とした相対可視透過率を
第５図に示す。また、各温度で焼成したそれぞれの膜の
屈折率を第６図に示す。The ultraviolet light film according to the present invention has a composition ratio of TlO2:CeO2 of 0.12, 0.4 and 2; TiO
A film consisting of only 2 was prepared and each film was heated at 500°C170
After firing at 0°C, 800°C, 900°C and 1000°C, the transmission spectrum was measured and the visible transmittance was calculated. 5
The relative visible transmittance is shown in FIG. 5, assuming that the visible transmittance upon firing at 00° C. is 1. Moreover, the refractive index of each film fired at each temperature is shown in FIG.
ＴｉＯ２膜では８００°Ｃ以降急激に透過率が減少して
いるのがわかる。これは膜中の結晶粒子が成長したため
に散乱が大きくなったのが原因である。これに対して、
ＣｅＯ□が含まれている本発明の紫外線カット膜につい
ても可視透過率の減少が表面的には観察されているが、
これは膜の屈折率増大による表面反射の増大に対応して
おり、散乱による透過率の減少ではないと考えられる。It can be seen that the transmittance of the TiO2 film decreases rapidly after 800°C. This is due to the growth of crystal grains in the film, which resulted in increased scattering. On the contrary,
Although a decrease in visible transmittance has been superficially observed for the ultraviolet cut film of the present invention containing CeO□,
This corresponds to an increase in surface reflection due to an increase in the refractive index of the film, and is not considered to be a decrease in transmittance due to scattering.
目視観察の結果では、ＴｉＯ２膜では８００℃以上で明
瞭な白濁が生しているか、ＣｅＯ２含有１１Ｍは透明な
ままであった１゜また、ＣｅＯ２含有膜の透過率の減少
量は、屈折率よりｄＩ算される反射率の増大量にほぼ一
致する。As a result of visual observation, clear cloudiness occurred in the TiO2 film at temperatures above 800°C, while the CeO2-containing 11M remained transparent. This almost matches the amount of increase in reflectance calculated by dI.
第１図は、実施例１の組成物による紫外線カット＋＋Ｔ
１の吸収特性を表わすグラフ。
第２図は、実施例２の組成物による紫外線カット膜の吸
収特性を表わすグラフ。
第３１７１は、本発明の紫外線カッ１〜膜と従来の紫外
線カッ１〜股の吸収特性を比較して表わしたグラフ。
第４図は、無反射設計を施こした本発明の紫外線カッ１
へ膜と１’ｉ０２膜の吸収特性を比較して表わしたグラ
フ。
第５図は、本発明の紫外線カッ１〜膜とＴｊ Ｏ２膜の
焼成温度による可視透過率の変化を比較して表わしたグ
ラフ。
第６図は、本発明の紫外線カッ１〜膜とＴ」０．膜の焼
成温度による屈折率の変化を比較して表わしたグラフ。
１、事件の表示
平成２年 特許願 第３２１０４８号
２、発明の名称
高耐熱性無色紫外線カット膜および該被膜を有する透明
カラス
３、補正をする者
事件との関係 特許出願人
名 称 （６２６）三菱マテリアル株式会社（外１名
）（平成２年１２月２０日付で名称および住所−括変更
済）４、代理人（〒１６４）
（発送臼 平成３年３月１２日）Figure 1 shows ultraviolet rays cut by the composition of Example 1.
Graph showing the absorption characteristics of No. 1. FIG. 2 is a graph showing the absorption characteristics of the ultraviolet cut film formed by the composition of Example 2. No. 3171 is a graph comparing the absorption characteristics of the ultraviolet ray film of the present invention and the conventional ultraviolet ray film. Figure 4 shows the ultraviolet light filter 1 of the present invention with a non-reflective design.
A graph showing a comparison of the absorption characteristics of the Heme membrane and the 1'i02 membrane. FIG. 5 is a graph showing a comparison of changes in visible transmittance depending on firing temperature of the ultraviolet ray film of the present invention and the Tj O2 film. FIG. 6 shows the ultraviolet ray film of the present invention and T'0. A graph showing a comparison of changes in refractive index depending on the firing temperature of the film. 1. Indication of the case 1990 Patent Application No. 321048 2. Name of the invention Highly heat-resistant colorless ultraviolet cut film and transparent crow having the film 3. Person making the amendment Relationship with the case Patent applicant name (626) Mitsubishi Material Co., Ltd. (1 other person) (Name and address changed as of December 20, 1990) 4, Agent (164) (Shipping date: March 12, 1991)
Claims (1)
ンとセリウムの重量比がそれぞれの酸化物換算で１：０
．０２〜１：４．５であるように有機溶媒に混合し、該
混合液を基板に塗布し、４００〜１０００℃で焼成する
ことにより得られる高耐熱性無色紫外線カット膜。 ２、請求項１に記載の高耐熱性紫外線カット膜であって
、チタンとセリウムの重量比がそれぞれの酸化物換算で
１：０．０２〜１：１．５であるもの。 ３、請求項１または請求項２に記載の高耐熱性紫外線カ
ット膜であって、焼成温度が８００〜１０００℃である
もの。 ４、先行するいずれかの請求項に記載の被膜を有する透
明ガラス。[Claims] 1. Each organometallic compound of titanium and cerium is prepared in such a manner that the weight ratio of titanium and cerium is 1:0 in terms of the respective oxides.
．． A highly heat-resistant colorless ultraviolet ray blocking film obtained by mixing in an organic solvent at a ratio of 02 to 1:4.5, applying the mixture to a substrate, and baking at 400 to 1000°C. 2. The highly heat-resistant ultraviolet cut film according to claim 1, wherein the weight ratio of titanium to cerium is 1:0.02 to 1:1.5 in terms of their respective oxides. 3. The highly heat-resistant ultraviolet cut film according to claim 1 or 2, wherein the firing temperature is 800 to 1000°C. 4. A transparent glass having a coating according to any of the preceding claims.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32104890A JPH04193744A (en) | 1990-11-27 | 1990-11-27 | High heat-resistant colorless ultraviolet cutting film and transparent glass having this coated film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32104890A JPH04193744A (en) | 1990-11-27 | 1990-11-27 | High heat-resistant colorless ultraviolet cutting film and transparent glass having this coated film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04193744A true JPH04193744A (en) | 1992-07-13 |
Family
ID=18128219
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32104890A Pending JPH04193744A (en) | 1990-11-27 | 1990-11-27 | High heat-resistant colorless ultraviolet cutting film and transparent glass having this coated film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04193744A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017094867A1 (en) * | 2015-12-02 | 2017-06-08 | 旭硝子株式会社 | Wavelength-selective transparent glass product |
-
1990
- 1990-11-27 JP JP32104890A patent/JPH04193744A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017094867A1 (en) * | 2015-12-02 | 2017-06-08 | 旭硝子株式会社 | Wavelength-selective transparent glass product |
| CN108473366A (en) * | 2015-12-02 | 2018-08-31 | 旭硝子株式会社 | Wavelength selective transmission glass article |
| JPWO2017094867A1 (en) * | 2015-12-02 | 2018-10-04 | Ａｇｃ株式会社 | Wavelength selective transmission glass article |
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