JPH0260397B2 - - Google Patents
Info
- Publication number
- JPH0260397B2 JPH0260397B2 JP4782081A JP4782081A JPH0260397B2 JP H0260397 B2 JPH0260397 B2 JP H0260397B2 JP 4782081 A JP4782081 A JP 4782081A JP 4782081 A JP4782081 A JP 4782081A JP H0260397 B2 JPH0260397 B2 JP H0260397B2
- Authority
- JP
- Japan
- Prior art keywords
- multilayer film
- producing
- organic titanium
- solution
- polymer solution
- 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.)
- Expired
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- 229920000642 polymer Polymers 0.000 claims description 22
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 17
- 239000010936 titanium Substances 0.000 claims description 17
- 229910052719 titanium Inorganic materials 0.000 claims description 17
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 13
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 2
- 150000003377 silicon compounds Chemical class 0.000 claims 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 239000010408 film Substances 0.000 description 21
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- -1 Ketone acids Chemical class 0.000 description 4
- 239000010409 thin film Substances 0.000 description 3
- ROWKJAVDOGWPAT-UHFFFAOYSA-N Acetoin Chemical compound CC(O)C(C)=O ROWKJAVDOGWPAT-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VTESCYNPUGSWKG-UHFFFAOYSA-N (4-tert-butylphenyl)hydrazine;hydrochloride Chemical compound [Cl-].CC(C)(C)C1=CC=C(N[NH3+])C=C1 VTESCYNPUGSWKG-UHFFFAOYSA-N 0.000 description 1
- CVBUKMMMRLOKQR-UHFFFAOYSA-N 1-phenylbutane-1,3-dione Chemical compound CC(=O)CC(=O)C1=CC=CC=C1 CVBUKMMMRLOKQR-UHFFFAOYSA-N 0.000 description 1
- SDVJLFHTPKRNAH-UHFFFAOYSA-N 2-ethyl-3-ketopentanoic acid Chemical compound CCC(C(O)=O)C(=O)CC SDVJLFHTPKRNAH-UHFFFAOYSA-N 0.000 description 1
- HXUIDZOMTRMIOE-UHFFFAOYSA-N 3-oxo-3-phenylpropionic acid Chemical compound OC(=O)CC(=O)C1=CC=CC=C1 HXUIDZOMTRMIOE-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N Acetoacetic acid Natural products CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical class O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001371 alpha-amino acids Chemical class 0.000 description 1
- 235000008206 alpha-amino acids Nutrition 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- WOWBFOBYOAGEEA-UHFFFAOYSA-N diafenthiuron Chemical compound CC(C)C1=C(NC(=S)NC(C)(C)C)C(C(C)C)=CC(OC=2C=CC=CC=2)=C1 WOWBFOBYOAGEEA-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- GFAZHVHNLUBROE-UHFFFAOYSA-N hydroxymethyl propionaldehyde Natural products CCC(=O)CO GFAZHVHNLUBROE-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D185/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Coating compositions based on derivatives of such polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
- Chemically Coating (AREA)
- Optical Elements Other Than Lenses (AREA)
- Optical Filters (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
Description
本発明は薄膜による光の干渉作用を利用したも
ので、基板上にTiO2／SiO2／TiO2の三層の被膜
を形成することによる光学的多層膜の製造方法に
関するものである。
ガラスなどの基板上に屈折率の高い被膜と低い
被膜を一定膜厚で交互にコーテイングすると特定
波長の光をより強く反射することは知られてい
る。この被膜形成方法としては、真空蒸着法やス
パツタリング法などが行なわれている。しかしこ
れらの方法では高温度・高真空を必要とし、装置
が高価であり、また膜厚コントロールなどの操作
が繁雑であり、大型処理が困難という欠点があつ
た。有機金属化合物溶液を使用する浸漬法はこれ
らにくらべ、より簡便な方法であるが、塗付時の
被膜の白濁、あるいは焼成後の被膜の強度が不十
分であるという欠点があつた。
本発明者らは、上記の欠点を改良した簡便な多
層膜の製造方法を見い出すべく研究した結果、本
発明を完成した。
本発明は、基板上にTiO2／SiO2／TiO2からな
る３層被膜をほどこす多層膜の製造において、基
板を有機チタンポリマー溶液で処理し、乾燥後有
機ケイ素化合物溶液で処理し、乾燥せしめ、さら
に有機チタンポリマー溶液で処理し、次に350゜〜
700℃の温度で加熱処理せしめることを特徴とす
る多層膜の製造方法である。
本発明において使用する有機チタンポリマー溶
液は、基板上にまたは基板上にTiO2／SiO2の被
膜を形成した表面に塗付し、乾燥後加熱処理せし
めることによるTiO2薄膜を形成し得るものであ
ればよく、例えば一般式
（Ｒは炭素数１〜18、好ましくは２〜４のアル
キル基であり、ｎは２〜10である。）
で示される有機チタンポリマーの有機溶剤溶液が
好ましい。上記有機チタンポリマーは、例えばテ
トラアルキルチタンを水により重合させることに
より得られる。有機チタンポリマー用の溶剤とし
ては炭素数８以下のアルコール類、エステル類、
エーテル類、炭化水素類、ハロゲン化炭化水素類
が用いられ、これらの溶剤中にアセチルアセト
ン、ベンゾイルアセトンなどのβ−ジケトン類、
アセト酢酸、プロピオニル酪酸、ベンゾイルギ
酸、ベンゾイル酢酸などのケトン酸類、該ケトン
酸類のエステル類、乳酸、グリコール酸、α−オ
キシ酪酸、サリチル酸などのオキシ酸類、該オキ
シ酸類のエステル類、ジアセトンアルコール、ア
セトインなどのオキシケトン類、グリシン、アラ
ニンなどのα−アミノ酸類及びアミノエチルアル
コールなどのアミノアルコール類からなる群から
選ばれる１種以上の化合物を、溶質が加熱処理さ
れてTiO2となつたときのTiO2換算でその１〜10
倍モル、好ましくは1.5〜３倍モル含有するもの
が溶液の安定性において優れており、また塗膜の
白濁防止効果の点で好ましい。溶剤の使用量は上
記TiO2換算濃度が１〜10重量％になるに相当す
る量である。これよりTiO2換算濃度が大きすぎ
ると被膜が厚くなりすぎて、加熱処理時にクラツ
クが入る可能性が高くなり、また小さすぎると充
分な膜厚が得られない。
本発明において使用する有機ケイ素化合物溶液
としては、TiO2被膜を有する基板上に塗付し、
乾燥後加熱処理せしめることによりSiO2薄膜を
形成し得るものであればよく、アルコキシシラン
を低級アルコール及び酢酸による希釈下、微量の
鉱酸を触媒として重合せしめて得られるシロキサ
ン化合物溶液が好ましい。有機ケイ素化合物の溶
媒としては、前記有機チタンポリマーの溶媒と同
種のものが使用できる。溶液の濃度としては
SiO2換算濃度で１〜12重量％である。これより
大きいと膜厚が厚くなりすぎて加熱処理時にクラ
ツクが入る可能性が高くなり、また小さすぎると
充分な膜厚が得られない。
第三層のTiO2膜形成用有機チタンポリマー溶
液は前記第一層用のものと同種のものが使用され
る。
本発明において、三層膜を被覆すべき基板とし
ては、ガラス、セラミツクス、金属等加熱処理に
耐えるものであれば、すべて適用可能である。
本発明において、基板を第１に有機チタンポリ
マー溶液で処理し、乾燥後、第２の有機ケイ素化
合物溶液で処理し、乾燥せしめ、さらに第３に有
機チタンポリマー溶液で処理し、第４に350゜〜
700℃の温度で加熱処理せしめる。上記各溶液に
よる処理方法としては、浸漬法、スピンナー法等
常法が適用できる。上記乾燥は基板上に塗付され
た溶液の溶媒を大部分揮発させればよい。
本発明においてTiO2膜及び又はSiO2膜の強度
を増加させるために、有機チタンポリマー溶液及
び又は有機ケイ素化合物溶液中にガラス質形成剤
として五酸化リンを加熱処理後に生成するTiO2
及び又はSiO2量を基準として0.5〜３重量％に相
当する量を添加することが好ましい。
本発明において得られる三層膜は、密着性、耐
衝撃性等物理的性質及び耐水性、耐アルカリ性等
化学的性質において、従来の方法によるものと比
較して優れている。
本発明において得られる三層膜被覆基板は反射
鏡、装飾用色ガラス、鏡、フイルターなどに使用
される。
以下に実施例を挙げて本発明を具体的に説明す
る。
有機チタンポリマー溶液の調製
平均的構造が
で示される有機チタンポリマー10重量部をメタノ
ール：アセチルアセトン：酢酸エチル＝36.5：
10：15（重量比）の混合溶媒に溶解せしめたTiO2
換算濃度4.8重量％の有機チタンポリマー溶液Ａ
及び該有機チタンポリマー溶液にP2O5をTiO2換
算濃度２重量％濃度に相当する量を添加した有機
チタンポリマー溶液Ｂを調製した。
別にテトラｎ−ブトキシチタン10重量部をメタ
ノール：アセチルアセトン：酢酸エチル＝36.5：
10：15（重量比）の混合溶媒に溶解せしめて有機
チタン溶液Ｃを調製した。
有機ケイ素化合物溶液の調製
テトラエトキシシラン219重量部、エタノール
643重量部、酢酸206重量部及び塩酸0.3重量部を
混合し、還流下で45時間反応させてSiO2換算濃
度5.9重量％の有機ケイ素化合物溶液Ｅを得た。
またこの有機ケイ素化合物溶液ＥにSiO2換算
重量の2.5重量％のP2O5を加え、有機ケイ素化合
物溶液Ｆを得た。
実施例１〜５及び対比例１〜２
第１表に示す条件でガラス基板を処理し、３層
被覆ガラス板を得、その特性を測定した。結果を
第１表に示す。
The present invention utilizes the light interference effect of a thin film, and relates to a method for producing an optical multilayer film by forming a three-layer film of TiO 2 /SiO 2 /TiO 2 on a substrate. It is known that when a substrate such as glass is alternately coated with a film with a high refractive index and a film with a low refractive index at a constant thickness, light of a specific wavelength is reflected more strongly. As a method for forming this film, a vacuum evaporation method, a sputtering method, etc. are used. However, these methods require high temperature and high vacuum, expensive equipment, and complicated operations such as film thickness control, making large-scale processing difficult. The immersion method using an organometallic compound solution is a simpler method compared to these methods, but it has drawbacks such as clouding of the coating upon application and insufficient strength of the coating after firing. The present inventors completed the present invention as a result of research to find a simple method for manufacturing a multilayer film that improves the above-mentioned drawbacks. In the production of a multilayer film in which a three-layer coating consisting of TiO 2 /SiO 2 /TiO 2 is applied on a substrate, the present invention involves treating the substrate with an organotitanium polymer solution, drying it, treating it with an organosilicon compound solution, and drying it. further treated with organic titanium polymer solution, and then heated at 350°~
This is a method for producing a multilayer film characterized by heat treatment at a temperature of 700°C. The organic titanium polymer solution used in the present invention can be applied to a substrate or a surface on which a TiO 2 /SiO 2 film has been formed, and then dried and then heat-treated to form a TiO 2 thin film. For example, a general formula (R is an alkyl group having 1 to 18 carbon atoms, preferably 2 to 4 carbon atoms, and n is 2 to 10.) An organic solvent solution of an organic titanium polymer represented by the following is preferred. The organic titanium polymer can be obtained, for example, by polymerizing tetraalkyl titanium with water. Solvents for organic titanium polymers include alcohols with 8 or less carbon atoms, esters,
Ethers, hydrocarbons, and halogenated hydrocarbons are used, and these solvents contain β-diketones such as acetylacetone and benzoylacetone.
Ketone acids such as acetoacetic acid, propionylbutyric acid, benzoylformic acid, and benzoylacetic acid, esters of the ketonic acids, oxyacids such as lactic acid, glycolic acid, α-oxybutyric acid, and salicylic acid, esters of the oxyacids, diacetone alcohol, One or more compounds selected from the group consisting of oxyketones such as acetoin, α-amino acids such as glycine and alanine, and amino alcohols such as aminoethyl alcohol are heated when the solute is converted into TiO2. 1 to 10 in terms of TiO 2
Those containing twice the mole, preferably 1.5 to 3 times the mole, are excellent in solution stability and are preferred from the viewpoint of preventing clouding of the coating film. The amount of the solvent used is an amount corresponding to the TiO 2 equivalent concentration of 1 to 10% by weight. If the TiO 2 equivalent concentration is too large, the film will become too thick, increasing the possibility of cracks occurring during heat treatment, and if it is too small, a sufficient film thickness will not be obtained. The organosilicon compound solution used in the present invention is applied onto a substrate having a TiO 2 coating,
Any material that can form a SiO 2 thin film by heat treatment after drying may be used, and a siloxane compound solution obtained by polymerizing an alkoxysilane diluted with a lower alcohol and acetic acid using a trace amount of mineral acid as a catalyst is preferred. As the solvent for the organosilicon compound, the same solvent as that for the organotitanium polymer can be used. As the concentration of the solution
The concentration is 1 to 12% by weight in terms of SiO 2 . If it is larger than this, the film thickness will be too thick and there is a high possibility that cracks will occur during heat treatment, and if it is too small, a sufficient film thickness will not be obtained. The organic titanium polymer solution for forming the third layer TiO 2 film is the same as that for the first layer. In the present invention, the substrate to be coated with the three-layer film may be any material that can withstand heat treatment, such as glass, ceramics, and metal. In the present invention, the substrate is first treated with an organotitanium polymer solution, dried, then treated with a second organosilicon compound solution, dried, thirdly treated with an organotitanium polymer solution, and fourthly treated with an organotitanium polymer solution.゜～
Heat treated at a temperature of 700℃. As a treatment method using each of the above solutions, conventional methods such as a dipping method and a spinner method can be applied. The above drying may be performed by volatilizing most of the solvent of the solution applied onto the substrate. In the present invention, in order to increase the strength of the TiO 2 film and/or SiO 2 film, phosphorus pentoxide is added as a glass forming agent in the organotitanium polymer solution and/or organosilicon compound solution after heat treatment .
It is preferable to add an amount corresponding to 0.5 to 3% by weight based on the amount of SiO 2 and/or SiO 2 . The three-layer film obtained in the present invention is superior to those produced by conventional methods in terms of physical properties such as adhesion and impact resistance, and chemical properties such as water resistance and alkali resistance. The three-layer film-coated substrate obtained in the present invention is used for reflective mirrors, decorative colored glass, mirrors, filters, and the like. The present invention will be specifically described below with reference to Examples. Preparation of organotitanium polymer solution.The average structure is 10 parts by weight of the organic titanium polymer shown in methanol: acetylacetone: ethyl acetate = 36.5:
TiO 2 dissolved in a mixed solvent of 10:15 (weight ratio)
Organic titanium polymer solution A with a converted concentration of 4.8% by weight
An organic titanium polymer solution B was prepared by adding P 2 O 5 to the organic titanium polymer solution in an amount corresponding to a concentration of 2% by weight in terms of TiO 2 . Separately, 10 parts by weight of tetra-n-butoxytitanium was added to methanol:acetylacetone:ethyl acetate=36.5:
Organic titanium solution C was prepared by dissolving it in a mixed solvent of 10:15 (weight ratio). Preparation of organosilicon compound solution 219 parts by weight of tetraethoxysilane, ethanol
643 parts by weight, 206 parts by weight of acetic acid and 0.3 parts by weight of hydrochloric acid were mixed and reacted under reflux for 45 hours to obtain organosilicon compound solution E having a concentration of 5.9% by weight in terms of SiO 2 . Furthermore, 2.5% by weight of P 2 O 5 based on SiO 2 equivalent weight was added to this organosilicon compound solution E to obtain an organosilicon compound solution F. Examples 1 to 5 and Comparative Examples 1 to 2 Glass substrates were treated under the conditions shown in Table 1 to obtain three-layer coated glass plates, and their properties were measured. The results are shown in Table 1.
【表】【table】
Claims (1)
膜をほどこす多層膜の製造において、基板を有機
チタンポリマー溶液で処理し、乾燥後有機ケイ素
化合物溶液で処理し、乾燥せしめさらに有機チタ
ンポリマー溶液で処理し、次に350〜700℃の温度
で加熱処理せしめることを特徴とする多層膜の製
造方法。 ２ 有機チタンポリマー溶液が一般式 （Ｒは炭素数２〜４のアルキル基であり、ｎは
２〜10である） で示される有機チタンポリマーのβ−ジケトン
類、ケトン酸類、ケトン酸エステル類を含む有機
溶媒溶液である特許請求の範囲第１項記載の多層
膜の製造方法。 ３ 有機ケイ素化合物がSi（OR）4〔Ｒはメチル基
またはエチル基〕で示される化合物をメタノール
あるいはエタノールと酢酸との反応において反応
系において重合せしめたものである特許請求の範
囲第１項記載の多層膜の製造方法。 ４ 有機チタンポリマー溶液及びまたは有機ケイ
素化合物溶液が五酸化リンを含有するものである
特許請求範囲第１項記載の多層膜の製造方法。 ５ 処理方法が浸漬法である特許請求の範囲第１
項、第２項、第３項または第４項記載の多層膜の
製造方法。[Claims] 1. In the production of a multilayer film in which a three-layer coating consisting of TiO 2 /SiO 2 /TiO 2 is applied on a substrate, the substrate is treated with an organic titanium polymer solution, and after drying, treated with an organic silicon compound solution. A method for producing a multilayer film, which comprises drying the film, treating it with an organic titanium polymer solution, and then heat-treating it at a temperature of 350 to 700°C. 2 The organic titanium polymer solution has the general formula (R is an alkyl group having 2 to 4 carbon atoms, and n is 2 to 10) The patent claim is an organic solvent solution containing β-diketones, ketonic acids, and ketonic acid esters of an organic titanium polymer represented by A method for producing a multilayer film according to item 1. 3. Claim 1, wherein the organosilicon compound is obtained by polymerizing a compound represented by Si(OR) 4 [R is a methyl group or an ethyl group] in a reaction system in a reaction between methanol or ethanol and acetic acid. A method for producing a multilayer film. 4. The method for producing a multilayer film according to claim 1, wherein the organic titanium polymer solution and/or the organic silicon compound solution contains phosphorus pentoxide. 5 Claim 1 in which the treatment method is a dipping method
The method for producing a multilayer film according to item 1, 2, 3, or 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4782081A JPS57161809A (en) | 1981-03-31 | 1981-03-31 | Manufacture of multilayered film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4782081A JPS57161809A (en) | 1981-03-31 | 1981-03-31 | Manufacture of multilayered film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57161809A JPS57161809A (en) | 1982-10-05 |
| JPH0260397B2 true JPH0260397B2 (en) | 1990-12-17 |
Family
ID=12785987
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4782081A Granted JPS57161809A (en) | 1981-03-31 | 1981-03-31 | Manufacture of multilayered film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57161809A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6184380A (en) * | 1984-10-01 | 1986-04-28 | Nitto Kasei Kk | Formation of conductive oxide tin film on base body |
| JPH0629882B2 (en) * | 1986-04-14 | 1994-04-20 | 東芝硝子株式会社 | Multilayer film mirror |
| JPH0786567B2 (en) * | 1987-01-24 | 1995-09-20 | 松下電工株式会社 | Method of manufacturing UV cut coating film |
| JPS63182603A (en) * | 1987-01-24 | 1988-07-27 | Matsushita Electric Works Ltd | Ultraviolet cut filter |
| JPH09220519A (en) * | 1996-02-16 | 1997-08-26 | Mitsubishi Paper Mills Ltd | Method for producing titanium oxide-containing laminated sheet |
| CN1115572C (en) * | 1998-02-18 | 2003-07-23 | 精工爱普生株式会社 | Method of fabricating distributed reflection multilayer mirror |
| CN104894535B (en) * | 2015-05-12 | 2017-04-26 | 浙江大学 | Method for preparing TiO2/SiO2 composite film for photoinduced cell detachment |
-
1981
- 1981-03-31 JP JP4782081A patent/JPS57161809A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57161809A (en) | 1982-10-05 |
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