JPS6214501B2 - - Google Patents
Info
- Publication number
- JPS6214501B2 JPS6214501B2 JP56204847A JP20484781A JPS6214501B2 JP S6214501 B2 JPS6214501 B2 JP S6214501B2 JP 56204847 A JP56204847 A JP 56204847A JP 20484781 A JP20484781 A JP 20484781A JP S6214501 B2 JPS6214501 B2 JP S6214501B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- paste
- organic solvent
- colored
- metal oxide
- 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
Links
- 238000000034 method Methods 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 7
- 150000002902 organometallic compounds Chemical class 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 239000000020 Nitrocellulose Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229920001220 nitrocellulos Polymers 0.000 claims description 5
- 238000007650 screen-printing Methods 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000009835 boiling Methods 0.000 claims 1
- 239000011248 coating agent Substances 0.000 claims 1
- 230000001747 exhibiting effect Effects 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 claims 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 3
- -1 alcohol ethers Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 2
- 229960001826 dimethylphthalate Drugs 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
- JXEMEZSWPQSCST-UHFFFAOYSA-J C(C)C(C(=O)[O-])CCCC.[W+4].C(C)C(C(=O)[O-])CCCC.C(C)C(C(=O)[O-])CCCC.C(C)C(C(=O)[O-])CCCC Chemical compound C(C)C(C(=O)[O-])CCCC.[W+4].C(C)C(C(=O)[O-])CCCC.C(C)C(C(=O)[O-])CCCC.C(C)C(C(=O)[O-])CCCC JXEMEZSWPQSCST-UHFFFAOYSA-J 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229940007550 benzyl acetate Drugs 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N methyl monoether Natural products COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
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
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/27—Oxides by oxidation of a coating previously applied
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Optical Filters (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
- Surface Treatment Of Glass (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
Description
本発明は、ガラス等の基板上に形成する着色皮
膜に係り、更に詳しくは、該着色皮膜が、遷移金
属酸化物よりなる膜厚１μｍ以下の皮膜に関する
もので、その用途はエレクトロクロミツク用の材
料、或いは液晶表示素子のカラーフイルターとし
て好適なものである。
従来この種の皮膜は、真空蒸着法、浸漬法等に
より形成されるのが一般的であつた。しかし、前
者の方法によれば、量産性に問題があり、又、パ
ターン化に対しては、エツチング等の余分な工程
を必要としていた。一方、後者の方法によれば、
量産性に問題は少ないが、パターン化対応につい
ては同様の問題をかかえていた。この様に従来方
法では、量産性、簡便さに欠ける所が多く、必ず
しも優れた方法とは言い難い面を有していた。
一方、スクリーン印刷法では係る問題はなく、
スクリーン印刷可能なペーストさえあれば、所望
の形状にスクリーン印刷し、焼成することで、目
的とする皮膜を所望の形状に形成可能である。し
かし、スクリーン印刷可能な優れたペーストは末
だ発表されていないというのが現状である。
本発明は、叙上のスクリーン印刷可能な優れた
印刷ペーストを提供するためになされたもので、
焼成により着色金属酸化物皮膜を形成し得る化合
物として、有機溶媒に可溶な、有機遷移金属化合
物を選択して、ペースト化に成功した所に特徴が
ある。更に詳しくは、Ｖ、Cr、Ni、Mn、Fe、
Coから選ばれた少くとも１種の有機金属化合物
を、沸点が150〜200℃の有機溶媒、例えば、オク
チルアルコール、ターピネオール、ペンジルアル
コール等のアルコール類、ベンジルアセテート、
ジメチルフタレート等のエステル類、カルビトー
ル、ブチルカルビトール、ブチルセロソルブ等の
アルコールエーテル類に溶解し、これに粘性剤と
してニトロセルローズ、を添加混合することによ
り、ペーストを作成する。このペーストを用いて
ガラス等の基板上にスクリーン印刷し400℃以上
の温度で焼成すると目的とする美しい着色皮膜が
所望の形状に形成される。形成された着色皮膜
は、使用した有機金属化合物の金属の種類等によ
つて、着色状態、比抵抗、皮膜強度等の特性が異
なるものが得られ、様々な応用が可能で極めて有
用である。以下、実施例に基づいて更に詳しく説
明する。
実施例 １
前記ペーストを作成するために有機金属化合物
としてアセチルアセトン（略号．Hacac）の配位
した有機金属錯体、例えば、Ｖ〓Ｏ（acac）2C〓ｒ
（acac）3、Ｎ〓ｉ（acac）2、Ｍ〓ｏ（acac）3、Ｆ〓
ｅ
（acac）3、Ｃ〓ｉ（acac）2、或いは金属の有機酸
塩、例えば２エチルヘキサン酸タングステンを使
用し、次に有機溶媒としてブチルカルビトール：
ブチルセロソルブ：ベンジルアセテート：ジメチ
ルフタレート＝４：２：２：２の混合溶媒系、更
に粘性剤としてニトロセルローズを夫々選択し、
前記有機金属化合物を前記有機溶媒に溶解し、こ
れに前記粘性剤を添加混合することによりペース
トを作成した。
次にこれ等のペーストを用いて、ステンレスネ
ツト250メツシユのスクリーン版を使用し、ガラ
ス基板上にスクリーン印刷し、150℃で20min.予
備乾燥し、更に500℃で30min.焼成して皮膜を形
成する。表にペースト組成と、得られた各々の
金属酸化物の皮膜の特性を示した。
The present invention relates to a colored film formed on a substrate such as glass, and more specifically, the colored film is a film made of a transition metal oxide and has a thickness of 1 μm or less, and is used for electrochromic applications. It is suitable as a material or a color filter of a liquid crystal display element. Conventionally, this type of film has generally been formed by a vacuum deposition method, a dipping method, or the like. However, the former method has problems in mass production and requires extra steps such as etching for patterning. On the other hand, according to the latter method,
There were few problems with mass production, but there were similar problems with patterning. As described above, the conventional methods often lack mass productivity and simplicity, and cannot necessarily be called excellent methods. On the other hand, the screen printing method does not have this problem.
As long as there is a screen-printable paste, the desired film can be formed in the desired shape by screen-printing it into the desired shape and baking it. However, the current situation is that no excellent paste that can be screen printed has been announced yet. The present invention was made to provide an excellent printing paste that can be screen printed as described above.
A distinctive feature of this method is that an organic transition metal compound that is soluble in an organic solvent was selected as the compound capable of forming a colored metal oxide film upon firing, and the paste was successfully formed. More specifically, V, Cr, Ni, Mn, Fe,
At least one organometallic compound selected from Co.
A paste is prepared by dissolving esters such as dimethyl phthalate and alcohol ethers such as carbitol, butyl carbitol, and butyl cellosolve, and adding and mixing nitrocellulose as a viscosity agent. When this paste is screen printed on a substrate such as glass and fired at a temperature of 400°C or higher, a beautiful colored film in the desired shape is formed. The formed colored film has different properties such as coloring state, specific resistance, film strength, etc. depending on the type of metal of the organometallic compound used, and is extremely useful as it can be used in a variety of applications. A more detailed explanation will be given below based on examples. Example 1 To prepare the paste, an organometallic complex coordinated with acetylacetone (abbreviation: Hacac), for example, V〓O(acac) 2 C〓 r
(acac) 3 , N〓 i (acac) 2 , M〓 o (acac) 3 , F〓
e
(acac) 3 , Ci (acac) 2 , or an organic acid salt of a metal, such as tungsten 2-ethylhexanoate, and then butyl carbitol as the organic solvent:
A mixed solvent system of butyl cellosolve: benzyl acetate: dimethyl phthalate = 4:2:2:2, further selecting nitrocellulose as a viscosity agent,
A paste was prepared by dissolving the organometallic compound in the organic solvent and adding and mixing the viscosity agent thereto. Next, using these pastes, screen printing was performed on a glass substrate using a stainless steel net 250 mesh screen plate, pre-drying at 150℃ for 20 minutes, and then baking at 500℃ for 30 minutes to form a film. do. The table shows the paste composition and the characteristics of each metal oxide film obtained.
【表】
表により明らかな通り、有機金属化合物の金
属の種類が変化すると、異なつた着色状態、電気
抵抗等を有する着色皮膜が得られることがわか
る。これ等の着色皮膜は、多方面への応用が可能
で極めて有用である。又、ニトロセルローズは他
のセルローズ化合物に比べ熱分解温度が約200℃
と低く、かつ爆発的な燃焼性を有しているため完
全な燃焼がおこなわれ、均一な膜特性をもつ品質
良好な焼成膜が得られる。
実施例 ２
実施例１、のペーストを使用し、400℃で
30min.焼成して得られた皮膜の特性は、前記実
施例と同様な結果を示した。
なお実施例１、において使用した各種のペース
トを適宜混合して混合ペーストを作成し、400℃
以上の温度で焼成すると、形成された皮膜の着色
状態は、単独ペーストの混合比に対応した中間色
が容易に得られる。
叙上如く本発明によれば、着色金属酸化物を形
成するためのペースト材料として有機金属化合物
を使用したもので、有機金属化合物が有機溶媒に
可溶であるために、スクリーン印刷に適したペー
ストが得られ、量産性に適し、所望のパターンの
形成が容易で、エレクトロクロミツクの材料、或
いは液晶表示素子のカラーフイルターとして好適
な皮膜を提供することが可能となる。又、粘性剤
としてニトロセルローズを添加して焼成するの
で、400〜500℃という比較的低温度で短時間に処
理ができ、ソーダガラス等からなるガラス基板を
溶融変形させることなく品質の優れた酸化物被膜
を効率良く量産することが可能となる。[Table] As is clear from the table, it can be seen that when the type of metal in the organometallic compound is changed, colored films having different colored states, electrical resistances, etc. can be obtained. These colored films can be applied in many fields and are extremely useful. Additionally, nitrocellulose has a thermal decomposition temperature of approximately 200°C compared to other cellulose compounds.
Because it has a low and explosive combustibility, complete combustion occurs and a fired film of good quality with uniform film properties can be obtained. Example 2 Using the paste of Example 1, at 400℃
The properties of the film obtained by firing for 30 minutes showed similar results to those of the above example. A mixed paste was prepared by appropriately mixing the various pastes used in Example 1, and heated at 400°C.
When fired at the above temperature, the colored state of the formed film can easily be a neutral color corresponding to the mixing ratio of the single paste. As described above, according to the present invention, an organometallic compound is used as a paste material for forming a colored metal oxide, and since the organometallic compound is soluble in an organic solvent, the paste is suitable for screen printing. It is possible to provide a film suitable for mass production, easy to form a desired pattern, and suitable as an electrochromic material or a color filter for a liquid crystal display element. In addition, since nitrocellulose is added as a viscous agent and fired, the process can be carried out in a short time at a relatively low temperature of 400 to 500°C, resulting in high-quality oxidation without melting and deforming glass substrates made of soda glass, etc. It becomes possible to mass-produce material coatings efficiently.
Claims (1)
も１種の金属の有機金属化合物に、ニトロセルロ
ーズと有機溶媒とを添加混合して成るペースト
を、絶縁性基板上にスクリーン印刷等によつて塗
布した後、該塗膜を焼成して酸化することによ
り、前記金属の酸化物に特有の色を呈する皮膜を
得ることを特徴とする着色金属酸化物皮膜の形成
方法。 ２ 有機溶媒として沸点が150〜250℃の有機溶媒
を使用したことを特徴とする特許請求の範囲第１
項記載の着色金属酸化物皮膜の形成方法。[Claims] 1. A paste made by adding and mixing nitrocellulose and an organic solvent to an organometallic compound of at least one metal selected from Cr, Ni, Mn, Fe, and Co, is applied to an insulating substrate. Formation of a colored metal oxide film, characterized in that a film exhibiting a color specific to the metal oxide is obtained by coating the film by screen printing or the like, and then baking and oxidizing the film. Method. 2 Claim 1, characterized in that an organic solvent with a boiling point of 150 to 250°C is used as the organic solvent.
A method for forming a colored metal oxide film as described in .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56204847A JPS58110444A (en) | 1981-12-18 | 1981-12-18 | Formation of colored metallic oxide film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56204847A JPS58110444A (en) | 1981-12-18 | 1981-12-18 | Formation of colored metallic oxide film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58110444A JPS58110444A (en) | 1983-07-01 |
| JPS6214501B2 true JPS6214501B2 (en) | 1987-04-02 |
Family
ID=16497372
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56204847A Granted JPS58110444A (en) | 1981-12-18 | 1981-12-18 | Formation of colored metallic oxide film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58110444A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0415497Y2 (en) * | 1986-11-20 | 1992-04-07 | ||
| US5384157A (en) * | 1991-12-20 | 1995-01-24 | Fuji Xerox Co., Ltd. | Tungsten oxide film, process for producing same and electrochromic device using same |
-
1981
- 1981-12-18 JP JP56204847A patent/JPS58110444A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58110444A (en) | 1983-07-01 |
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