JPS63161156A - Thin hard blue film and its production - Google Patents
Thin hard blue film and its productionInfo
- Publication number
- JPS63161156A JPS63161156A JP31053286A JP31053286A JPS63161156A JP S63161156 A JPS63161156 A JP S63161156A JP 31053286 A JP31053286 A JP 31053286A JP 31053286 A JP31053286 A JP 31053286A JP S63161156 A JPS63161156 A JP S63161156A
- Authority
- JP
- Japan
- Prior art keywords
- film
- tio
- hard
- vacuum chamber
- gas
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 4
- 239000010408 film Substances 0.000 claims description 38
- 239000010409 thin film Substances 0.000 claims description 17
- 238000001704 evaporation Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 3
- -1 l_2O_3 Chemical class 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052593 corundum Inorganic materials 0.000 abstract description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 7
- 229910009973 Ti2O3 Inorganic materials 0.000 abstract description 6
- GQUJEMVIKWQAEH-UHFFFAOYSA-N titanium(III) oxide Chemical compound O=[Ti]O[Ti]=O GQUJEMVIKWQAEH-UHFFFAOYSA-N 0.000 abstract description 6
- 238000010894 electron beam technology Methods 0.000 abstract description 4
- 238000001771 vacuum deposition Methods 0.000 abstract description 3
- 238000010849 ion bombardment Methods 0.000 abstract description 2
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 2
- 239000010935 stainless steel Substances 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract 3
- 239000007789 gas Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 2
- 241000269851 Sarda sarda Species 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
Landscapes
- Physical Vapour Deposition (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
この発明は、真空蒸着、スパッタリング、あるいはイオ
ングレーティングによって時計部品、筆記具、装身具、
各種装飾品等に被覆形成される硬質青色薄膜、およびそ
の製造方法に関するものである。[Detailed Description of the Invention] <Industrial Application Field> The present invention is applicable to watch parts, writing instruments, personal accessories,
The present invention relates to a hard blue thin film that is coated on various decorative items, etc., and a method for producing the same.
〈従来技術、その問題点〉
従来、真空中での蒸着、スパッタリング、あるいはイオ
ングレーティングを用いてＳ４０とｃｒとの組合せから
なる干渉膜、あるいはＴＩＯ２の干渉膜によって硬質青
色薄膜を形成していた。これらの干渉膜は光学距離で２
Ｏ０乃至：ｓｏｏｎｍ （ナノメートル）の厚さによ
って得られるものであるので、膜の分布が極めて均一で
なければ池の色が混ってしまう欠点があった。このため
、複雑な形状の品物を同時に多量処理することができな
かった。また、充分に満足できる硬質薄膜を得ることが
できず、製品の附摩耗性に問題があった。<Prior art and its problems> Conventionally, a hard blue thin film has been formed using vacuum deposition, sputtering, or ion grating with an interference film made of a combination of S40 and Cr, or an interference film of TIO2. These interference films have an optical distance of 2
Since it is obtained with a thickness of O0 to nanometers (nanometers), there is a drawback that the color of the pond will be mixed unless the distribution of the film is extremely uniform. For this reason, it has been impossible to process a large number of products with complex shapes at the same time. In addition, it was not possible to obtain a sufficiently satisfactory hard thin film, and there was a problem with the abrasion resistance of the product.
く問題点を解決するための手段〉
この発明は上記のような問題を解決した硬質青色薄膜お
よびその製造方法を提供することを目的としたものであ
る。Means for Solving the Problems> The object of the present invention is to provide a hard blue thin film that solves the above problems and a method for manufacturing the same.
この発明による硬質青色薄膜は、好ましくは最終的に形
成される薄膜の表面から約５μｍ（ミクロン）以内にＴ
ｉ ２Ｏ８、ＴＩＯ、またはＴ１□０８とＴＩＯの混合
物（Ｔ ｉ ２Ｏ３ ／Ｔ４０と示す）を主成分とし、
それに超硬質のＴ ＋ ＸＮ Ｉ −ｘ 、 Ｔ １ｘ
Ｃ＋−ｘのいずれか一方または両方を適当に混合して成
膜するか、あるいはン。The hard blue thin film according to the present invention preferably has a T
The main component is i 2O8, TIO, or a mixture of T1□08 and TIO (denoted as T i 2O3 /T40),
And super hard T + XN I -x, T 1x
Either one or both of C+-x may be appropriately mixed to form a film.
丁２Ｏ１．Ｔｉ０、またはＴｉ−２Ｏ３とＴｉＯの混合
物、すなわちＴｉ、 ２Ｏ３ ／ ＴＩ Ｏを主成分と
した被膜を透明で硬質のＡｌ２Ｏ３、Ｓ ＋ ０２、Ｚ
鰹Ｏ２などの酸化物の保護被膜で被覆して形成される。Ding2O1. Ti0, or a mixture of Ti-2O3 and TiO, i.e., a film mainly composed of Ti,2O3/TIO, is coated with transparent and hard Al2O3, S+02, Z
It is formed by coating with a protective coating of oxide such as bonito O2.
青色を呈する被膜を表面から５μｍ以内にあるように形
成するのが望ましい理由は、膜厚が５μｍ以上になると
、表面には青色の発色に叛全く寄与しない透明膜が形成
されることを意味し、経済的に問題７ｊＸあるからであ
る。The reason why it is desirable to form a blue coating within 5 μm from the surface is that if the film thickness exceeds 5 μm, a transparent film will be formed on the surface that does not contribute to blue color development at all. This is because there is an economic problem.
〈実施例の説明〉
以下、図示の実施例によってこの発明の詳細な説明する
０１は真空槽、２は真空ポンプ、３は真空槽１にＡｒ、
、Ｈ２またはＣ２Ｈ２、Ｏ□等の反応ガスを供給する反
応ガス供給系で、それぞれの反応ガスは流量制御弁４．
５．６を経て真空槽１に供給される。真空槽１内の底部
中央部には後程説明するように、Ｔｉ、Ａｌ２Ｏ３等の
被蒸発物７が充填されたるつぼ８が設置され、被蒸発物
７は電子銃９からの電子ビームｌＯによる衝撃によって
蒸発させられる。るつぼ８の近傍には熱電子放射電極１
１が設けられており、またるつぼ８の上面から例えば３
０ｆｆ乃至６０Ｍ上方にはイオン化電極１２が設置され
ている０また、るつぼ８の上方部、例えばるつぼ８の上
面から２５０ｆｆ乃至７００Ｍ上方には被処理物支持電
極１３が配置され、該被処理物支持電極１３によって被
処理物１４がるつぼ８と対向して支持されている。１５
は熱電子放射電極用の電源、１６はイオン化電極１２に
４０乃至４５Ｖの正電圧を供給することのでキル電源、
１７ハ被処理物１４Ｋ −１００Ｖ 乃至−１５００Ｖ
の電圧を供給する°ことのできる電源、１８は被処理物
加熱用ヒータである。<Description of Embodiments> Hereinafter, the present invention will be explained in detail with reference to the illustrated embodiments. 01 is a vacuum chamber, 2 is a vacuum pump, 3 is a vacuum chamber 1 with Ar,
, H2 or C2H2, O□, etc., each reactant gas is supplied to a flow rate control valve 4.
It is supplied to the vacuum chamber 1 through 5.6. As will be explained later, a crucible 8 filled with a substance 7 to be evaporated such as Ti, Al2O3, etc. is installed in the center of the bottom of the vacuum chamber 1, and the substance 7 to be evaporated is bombarded by an electron beam 1O from an electron gun 9. evaporated by Near the crucible 8 is a thermionic emission electrode 1.
1 is provided, and from the upper surface of the crucible 8, for example, 3
An ionization electrode 12 is installed above the crucible 8, for example, between 250ff and 700M above the top surface of the crucible 8. A workpiece 14 is supported by the electrode 13 so as to face the crucible 8 . 15
16 is a power supply for the thermionic emission electrode; 16 is a kill power supply for supplying a positive voltage of 40 to 45 V to the ionization electrode 12;
17C Processed object 14K -100V to -1500V
18 is a heater for heating the object to be processed.
〈動作ならびに作用〉 （実施例１） （イ）上記の装置において、るつぼ８にＴ１を入れる。<Operation and action> (Example 1) (a) In the above apparatus, put T1 into the crucible 8.
真空槽ｌを真空ポンプ２で１０−５乃至１０−’ Ｔｏ
ｒｒに排気し、ヒータ１８によって例えばステンレス鋼
からなる被処理物１４を２Ｏ０乃至２５０”Ｃに加熱し
て充分にガス出しする。10-5 to 10-' To
The workpiece 14 made of, for example, stainless steel is heated to 200 to 250''C by the heater 18 to sufficiently vent the gas.
（切次に電源１７を調整して被処理物１４に−４５０乃
至−ａｏｏｖの負電圧を印加し、制御弁４を開いて真空
槽ｌへの導入ガスとしてＡ−を約１Ｏ−２ＴＯｒｒに維
持しながら供給し、ｌＯ乃至１５分間Ａ、のイオンボン
バードによって被処理物の表面を清浄化する。(Next, adjust the power supply 17 to apply a negative voltage of -450 to -aoov to the workpiece 14, open the control valve 4, and maintain A- as the gas introduced into the vacuum chamber 1 at approximately 1O-2 TOrr. The surface of the object to be treated is cleaned by ion bombardment of lO to A for 15 minutes.
（ハ）次にＡｐの供給を停止し、被処理物１４の印加電
圧を−４００〜−４５０ｖとし、また電源１６を調整し
てイオン化電極１２に４０〜４５Ｖの正電圧を印加する
。(c) Next, the supply of Ap is stopped, the voltage applied to the object 14 is set to -400 to -450V, and the power supply 16 is adjusted to apply a positive voltage of 40 to 45V to the ionization electrode 12.
真空ポンプ２を動作させて真空槽１内を１０−５乃至１
０ Ｔｏｒｒに排気した後、電子ビーム１０による衝
撃によってるつぼ８内のＴ１を蒸発させ、且つ上記イオ
ン化電極１２によって蒸発Ｔｉをイオン化させる。Operate the vacuum pump 2 to increase the inside of the vacuum chamber 1 from 10-5 to 1
After evacuation to 0 Torr, the T1 in the crucible 8 is evaporated by impact with the electron beam 10, and the evaporated Ti is ionized by the ionization electrode 12.
これによって被処理物１４にＴ１膜を５００−１０００
人付着させる。As a result, 500 to 1000 T1 films are applied to the object 14 to be treated.
Attach people.
に）こ−で被処理物１４の温度が過度に上昇するのを防
止するために、該被処理物の印加電圧を−１００乃至−
２Ｏ０■に低下させ、さらにＴｉを蒸発させて、被処理
物１４上に全体で１０００乃至２Ｏ００人のＴｉ膜のみ
を付着させる。(b) In order to prevent the temperature of the workpiece 14 from rising excessively, the voltage applied to the workpiece 14 is set to -100 to -100.
The temperature is reduced to 200 cm, and Ti is further evaporated, so that only a total of 1000 to 2000 Ti films are deposited on the object 14 to be treated.
（旬その後、制御弁５を開いて真空槽ｌ内の圧力が５ｘ
ｌｏ−４乃至Ｉ Ｘｌ０−’ ＴＯｒｒ程度となるよう
にＮ２を導入し、蒸発Ｔｉとの反応によって被処理物１
４上に５０００乃至７０００人の硬質のＴｉ−ｘＮ、−
Ｘの被膜層を形成する。(After that, the control valve 5 is opened and the pressure inside the vacuum chamber 1 is increased to 5x.
N2 is introduced to a level of about lo-4 to I Xl0-' TOrr, and the material to be treated 1
5000 to 7000 hard Ti-xN on 4, -
A coating layer of X is formed.
（へ）Ｎ２ガスはそのま＼供給し続けて制御弁６を開い
て０２ガスを真空槽ｌ内の圧力が５Ｘ１０−’乃至７×
１０” ’ｒｏｒｒになるように導入し、同時にイオン
化電極１２に流れる電流がＩＯＡ程度になるように電源
ユ６を調整してＴｉの蒸発速度を低下させる。このよう
にしてさらに約２Ｏ００人成膜する。(F) Continue to supply N2 gas as it is, open control valve 6, and supply 02 gas until the pressure in the vacuum chamber 1 ranges from 5X10-' to 7X.
At the same time, the power supply unit 6 is adjusted so that the current flowing through the ionization electrode 12 is about IOA to reduce the evaporation rate of Ti.In this way, approximately 2000 more people were deposited. do.
以上の処理により、ＴｉｘＮｌ、４ ＋ Ｔｉ２Ｏ３／
Ｔｉ○の混合膜が得られた。この混合膜は極めて硬質の
青色薄膜となった。Through the above processing, TixNl,4 + Ti2O3/
A mixed film of Ti○ was obtained. This mixed film became an extremely hard blue thin film.
上記（旬および（へ）の工程でＮ２ガスの代りにＣ２Ｈ
２ガスを導入すれば、ＴｉｘＣ，工＋Ｔｉ２Ｏ３／Ｔｉ
ｅ、の混合膜からなる上記と同様な硬質の青色膜が得ら
れるＯＮ２ガスとＣ２Ｈ２ガスとを混合して供給すると
、Ｔ ｉ ２Ｏ ａ ／ Ｔ ｉ Ｏを主成分とし、”
ＸＮＩ−ＸとＴ ： ｘ Ｃ＋ −ｘの双方との混合膜
からなる硬質青色薄膜が得られた０
上記の工程中、熱電子放射電極１１を動作させて熱電子
を放射することによって光沢をもった被膜を形成するこ
とができた。C2H instead of N2 gas in the above (Shun and (to) steps)
If two gases are introduced, TixC, +Ti2O3/Ti
When ON2 gas and C2H2 gas are mixed and supplied, a hard blue film similar to the above made of a mixed film of e.
A hard blue thin film consisting of a mixed film of both XNI-X and T: It was possible to form a film with a high temperature.
（実施例２〕
上記イ）乃至に）の工程によって被処理物１４上にＴ１
膜を形成した後、被処理物１４の印加電圧を一５０Ｖ程
度とし、Ｔ（の蒸発速度をイオン化電極１２に流れる電
流がＩＯＡ程度になるように低下させ、同時に制御弁６
を開いて０２ガスを真空槽１内の圧力が５Ｘ １０”乃
至７ Ｘｌ０−’ Ｔｏｒｒになるように導入して、被
処理物１４上にＴ ｉ ２Ｏａ ／ ＴＩ Ｏ膜を形成
する。(Example 2) T1
After forming the film, the voltage applied to the object to be treated 14 is set to about -50V, the evaporation rate of T is reduced so that the current flowing through the ionization electrode 12 is about IOA, and at the same time the control valve 6 is
is opened and 02 gas is introduced so that the pressure within the vacuum chamber 1 becomes 5X10" to 7X10-' Torr, thereby forming a Ti2Oa/TIO film on the object to be processed 14.
次にるつぼ８に被蒸発物７としてＡｌ２Ｏ３を充填し、
再度真空ポンプ２をｗＪｆ′￥＝させつ父真空槽１内に
０２ガスを３ ＸＩＯ”乃至５ Ｘ １０−’ Ｔｏｒ
ｒになるように導入しながらるつぼ８のＡｌ２Ｏ３を電
子ビーム１゜で蒸発させることによシ上記Ｔ１゜０３／
ＴｉＯ膜上にＡｌ２Ｏ３の透明膜を形成する。Next, the crucible 8 is filled with Al2O3 as the material to be evaporated 7,
Turn on the vacuum pump 2 again and fill the vacuum chamber 1 with 02 gas from 3 XIO" to 5 X 10-' Tor
By evaporating Al2O3 in the crucible 8 with an electron beam of 1° while introducing it so that
A transparent film of Al2O3 is formed on the TiO film.
青色の比較的軟いＴｉ２Ｏ３／Ｔｉ○膜は透明でしかも
硬質のＡｌ２Ｏ８膜によって保護され、またＡ１２ｏ３
膜は２１１ｍ以上では干渉色を生じないことから、全体
として耐摩耗性に優れた美麗な青色薄膜を形成すること
ができる。The blue relatively soft Ti2O3/Ti○ film is protected by a transparent yet hard Al2O8 film, and the A12o3
Since the film does not produce interference color at a length of 211 m or more, a beautiful blue thin film with excellent wear resistance as a whole can be formed.
Ａｌ２Ｏ８ノ代りに被蒸発物としてＳ＋０２、Ｚｒ、０
２を２ 用ｆ しｄ Ｔ ｉ○／Ｔｏｏ膜上に硬質で透
明な５１０２、Ｚｒ Ｏ２膜が形成された硬質青色薄膜
が形成される。S+02, Zr, 0 as evaporable substances instead of Al2O8
2 to 2 f d A hard blue thin film is formed in which a hard and transparent 5102, Zr O2 film is formed on the Ti○/Too film.
なお、被蒸発物としての封の代りにＴｌＯ２を使用して
も同様な硬質青色薄膜が得られる。Note that a similar hard blue thin film can be obtained even if TlO2 is used instead of the seal as the substance to be evaporated.
く効 果〉
この発明によれば、複雑な形状をもった物品に対しても
混色のない極めて硬質で美麗な青色薄膜を容易に形成す
ることができ、時計部品、眼鏡、筆記具、装身具、各種
の装飾品に施こされる硬質青色薄膜として最適である。Effects> According to the present invention, it is possible to easily form an extremely hard and beautiful blue thin film without color mixing even on articles with complicated shapes, such as watch parts, eyeglasses, writing implements, jewelry, and various other items. It is ideal as a hard blue thin film applied to decorative items.
図はこの発明による硬質青色薄膜を形成するために使用
される真空蒸着装置の概略図である。
ユ・・・真空槽、２・・・真空ポンプ、３・・・反応ガ
ス系、７・・・被蒸発物、１４・・・被処理物。The figure is a schematic diagram of a vacuum deposition apparatus used to form a hard blue thin film according to the present invention. U... Vacuum chamber, 2... Vacuum pump, 3... Reactive gas system, 7... Evaporation target, 14... Processing target.
Claims (3)
形成されたＴｉ＿２Ｏ＿３、ＴｉＯ／またはＴｉ＿２Ｏ
＿３とＴｉＯとの混合物を主成分とする膜（Ｔｉ＿２Ｏ
＿３／ＴｉＯ膜）およびＴｉ＿ｘＮ＿１＿−＿ｘ、Ｔｉ
＿ｘＣ＿１＿−＿ｘのいずれか一方または両方との混合
膜、あるいはＴｉ＿２Ｏ＿３／ＴｉＯ膜とその上に形成
されたＡｌ＿２Ｏ＿３、ＳｉＯ＿２、ＺｒＯ＿２等の酸
化物の透明硬質膜とからなる硬質青色薄膜。(1) Ti_2O_3, TiO/or Ti_2O preferably formed within 5 microns from the surface of the final thin film
A film whose main component is a mixture of _3 and TiO (Ti_2O
_3/TiO film) and Ti_xN_1_-_x, Ti
A hard blue thin film consisting of a mixed film with one or both of _xC_1_-_x, or a Ti_2O_3/TiO film and a transparent hard film of an oxide such as Al_2O_3, SiO_2, ZrO_2 formed thereon.
いはＴｉＯ＿２からなる被蒸発物を蒸発させて該真空槽
中に配置された被処理物上にＴｉ被膜を形成する段階と
、上記真空槽中にＮ＿２ガスまたはＣ＿２Ｈ＿２ガスの
少なくとも一方を上記真空槽内の圧力が第２の所定圧力
となるように導入しつゝ引続き上記Ｔｉを蒸発させて上
記Ｔｉ被膜の表面にＴｉ＿ｘＮ＿１＿−＿ｘまたはＴｉ
＿ｘＣ＿１＿−＿ｘの少なくとも一方からなる被膜を形
成すると共に上記真空槽中にＮ＿２ガスまたはＣ＿２Ｈ
＿２ガスの少なくとも一方とＯ＿２ガスとを上記真空槽
内の圧力が第３の所定圧力となるように導入しつゝ引続
き上記Ｔｉを蒸発させてＴｉ＿ｘＮ＿１＿−＿ｘまたは
Ｔｉ＿ｘＣ＿１＿−＿ｘの少なくとも一方とＴｉ＿２Ｏ
＿３／ＴｉＯとの混合膜を形成する段階と、からなる硬
質青色薄膜の製造方法。(2) evaporating a material to be evaporated consisting of Ti or TiO_2 in a first vacuum chamber evacuated to a predetermined pressure to form a Ti film on the material to be processed placed in the vacuum chamber; At least one of N_2 gas or C_2H_2 gas is introduced into the vacuum chamber so that the pressure in the vacuum chamber becomes a second predetermined pressure, and the Ti is subsequently evaporated to coat the surface of the Ti film with Ti_xN_1_-_x or Ti
A coating consisting of at least one of _xC_1_-_x is formed, and at the same time, N_2 gas or C_2H is
At least one of the _2 gas and O_2 gas are introduced so that the pressure in the vacuum chamber becomes a third predetermined pressure, and the Ti is subsequently evaporated to form at least one of Ti_xN_1_-_x or Ti_xC_1_-_x and Ti_2O.
A method for producing a hard blue thin film, comprising the step of forming a mixed film with _3/TiO.
いはＴｉＯ＿２からなる被蒸発物を蒸発させて該真空槽
中に配置された被処理物上にＴｉ被膜を形成する段階と
、上記真空槽中にＯ＿２ガスを該真空槽内の圧力が第２
の所定圧力となるように導入しつゝ引続き上記Ｔｉを蒸
発させて上記Ｔｉ被膜上にＴｉ＿２Ｏ＿３／ＴｉＯ被膜
を形成する段階と、上記真空槽中にＯ＿２ガスを該真空
槽内の圧力が第３の所定圧力となるように導入しつゝＡ
ｌ＿２Ｏ＿３、ＳｉＯ＿２、ＺｒＯ＿２等の金属酸化物
を蒸発させて上記Ｔｉ＿２Ｏ＿３／ＴｉＯ被膜の表面に
上記Ａｌ＿２Ｏ＿３、ＳｉＯ＿２、ＺｒＯ＿２等の硬質
透明被膜を形成する段階と、からなる硬質青色薄膜の製
造方法。(3) evaporating a material to be evaporated consisting of Ti or TiO_2 in a first vacuum chamber evacuated to a predetermined pressure to form a Ti film on the material to be processed placed in the vacuum chamber; O_2 gas is introduced into the vacuum chamber until the pressure inside the vacuum chamber reaches the second level.
a step of evaporating the Ti to form a Ti_2O_3/TiO film on the Ti film; A.
A method for producing a hard blue thin film, comprising the step of evaporating a metal oxide such as l_2O_3, SiO_2, ZrO_2, etc. to form a hard transparent film such as Al_2O_3, SiO_2, ZrO_2, etc. on the surface of the Ti_2O_3/TiO film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31053286A JPS63161156A (en) | 1986-12-24 | 1986-12-24 | Thin hard blue film and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31053286A JPS63161156A (en) | 1986-12-24 | 1986-12-24 | Thin hard blue film and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63161156A true JPS63161156A (en) | 1988-07-04 |
Family
ID=18006364
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31053286A Pending JPS63161156A (en) | 1986-12-24 | 1986-12-24 | Thin hard blue film and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63161156A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01279746A (en) * | 1988-05-06 | 1989-11-10 | Seiko Instr Inc | Outer ornament parts |
| US5225382A (en) * | 1991-04-03 | 1993-07-06 | Nisshin Steel Co. Ltd | Titanium oxide film |
| EP0926257A1 (en) * | 1997-12-23 | 1999-06-30 | United Technologies Corporation | Pre-oxidation method |
| JP2007254849A (en) * | 2006-03-24 | 2007-10-04 | Citizen Tohoku Kk | Metallic oxide film, and member coated with the metallic oxide film |
| JP2007254851A (en) * | 2006-03-24 | 2007-10-04 | Citizen Tohoku Kk | Metallic oxide film, and member coated with the metallic oxide film |
-
1986
- 1986-12-24 JP JP31053286A patent/JPS63161156A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01279746A (en) * | 1988-05-06 | 1989-11-10 | Seiko Instr Inc | Outer ornament parts |
| US5225382A (en) * | 1991-04-03 | 1993-07-06 | Nisshin Steel Co. Ltd | Titanium oxide film |
| EP0926257A1 (en) * | 1997-12-23 | 1999-06-30 | United Technologies Corporation | Pre-oxidation method |
| JP2007254849A (en) * | 2006-03-24 | 2007-10-04 | Citizen Tohoku Kk | Metallic oxide film, and member coated with the metallic oxide film |
| JP2007254851A (en) * | 2006-03-24 | 2007-10-04 | Citizen Tohoku Kk | Metallic oxide film, and member coated with the metallic oxide film |
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