JP2004237240A

JP2004237240A - Film forming method and apparatus

Info

Publication number: JP2004237240A
Application number: JP2003030992A
Authority: JP
Inventors: Nobuo Ishii; 信雄石井
Original assignee: Tokyo Electron Ltd
Current assignee: Tokyo Electron Ltd
Priority date: 2003-02-07
Filing date: 2003-02-07
Publication date: 2004-08-26

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of forming a DLC (diamond-like carbon) film on an interior surface of a vessel, not by a plasma film forming method. <P>SOLUTION: Solution for film formation, prepared by adding a fluoride ion supplement to an aqueous solution of at least one compound selected from a metal fluoride and a fluoro complex compound of a rare-earth metal, or a hydrofluoric acid solution of the above compound, is injected into a vessel 1, by which the solution for film formation contacts with the interior surface of the vessel and is discharged from the vessel 1 after a predetermined time is passed. An oxide of the solution is deposited on the internal surface of the vessel 1 to form an oxide film in a thin film shape. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【０００１】
【発明の属する技術分野】
本発明は，容器の表面に成膜するための方法及びその装置に関するものである。
【０００２】
【従来の技術】
近年，ペットボトルと呼ばれるポリエチレンテレフタレートからなるプラスティック容器が大量に流通しているが，容器内に充填する飲料が高温の飲料の場合には，容器を通じて該飲料の酸化が進むため，容器の内側表面に，ＤＬＣ（ＤｉａｍｏｎｄＬｉｋｅＣａｒｂｏｎ）膜，又はＳｉ含有ＤＬＣ膜をプラズマプロセスによって成膜することが行われている。
【０００３】
従来，ペットボトルのような容器の内側表面に，前記ＤＬＣ膜やＳｉ含有ＤＬＣ膜を成膜するにあたっては，容器の外側を囲み，減圧チャンバーを兼ねた外部電極を容器外側に配置するとともに，容器の内部に内部電極を配置し，容器の内側に原料ガスを導入し，外部電極に高周波を印加して容器内にプラズマを発生させて，容器の内側表面に所定の成膜処理を施す，いわゆるプラズマＣＶＤ方法が採用されている（例えば，特許文献１参照。）。
【０００４】
【特許文献１】
特開２００１−３３５９４６号公報
【０００５】
【発明が解決しようとする課題】
しかしながら，前記従来の方法は，実施するための装置自体が複雑であり，真空ポンプ，整合をとるためのマッチングボックスを用意しなければならず，また容器の外形に合わせてその都度形状の異なった外部電極も別途用意する必要があった。また所定の減圧度に達するために時間がかかり，単位時間あたりの生産量も満足できるものではなかった。しかも容器内に配置する内部電極表面も成膜されるため，定期的に内部電極をクリーニングするという煩瑣もあった。さらに外部電極の構造から，適用できる容器の形状が限られていた。
【０００６】
本発明はかかる点に鑑みてなされたものであり，前記したペットボトルのような容器の表面に成膜をするにあたり，そのようなプラズマＣＶＤ方法を用いずに，取り扱いが容易で，かつより生産性の高い成膜方法及びその装置を提供することを目的としている。
【０００７】
【課題を解決するための手段】
前記目的を達成するため，本発明は，容器の内側表面に被膜を形成する成膜方法であって，成膜対象とする前記容器の中に，成膜用溶液としての希土類金属のフルオロ錯化合物及び金属フッ化物から選ばれた少なくとも１種の化合物の水溶液，又は該化合物のフッ化水素酸溶液を注入して容器内側表面と前記成膜用溶液を接触させ，所定時間経過後，前記成膜用溶液を容器の外に排出することを特徴とするものである。
【０００８】
本発明によれば，容器内に希土類金属のフルオロ錯化合物及び金属フッ化物から選ばれた少なくとも１種の化合物の水溶液，又は該化合物のフッ化水素酸溶液にフッ化物イオン補足剤を加えたもの，を注入して容器内周と前記成膜用溶液を接触させるようにしたので，容器の内側表面にこれら水溶液中の酸化物が析出して薄膜が形成される。
【０００９】
たとえばフッ酸＋ＺｒＯ_２の溶液にホウ酸（ＢｒＯ_３）を加えたものを使用した場合，容器の内側表面には，ＺｒＯ_２の薄膜が形成される。
化学平衡で示せば，式（１），（２）に示したとおりである。なお具体的な反応プロセスについては，八木健「Ｓｙｎｔｈｅｓｉｓｏｆｆｕｎｃｔｉｏｎａｌｃｅｒａｍｉｃｍａｔｅｒｉａｌｓｆｒｏｍａｑｕｅｏｕｓｓｏｌｕｔｉｏｎｓ」（ＪＭａｔｅｒ．Ｒｅｓ．Ｖｏｌ．１３Ｎｏ．５Ｍａｙ１９９８）に詳しい。
【００１０】
【数１】

【００１１】
したがって，従来のようなプラズマＣＶＤによる成膜方法によらなくとも，容器の内側表面にこれら酸化物の薄膜が形成できる。
【００１２】
本発明に適した成膜用溶液としての希土類金属のフルオロ錯化合物及び金属フッ化物から選ばれた少なくとも１種の化合物の水溶液としては，たとえば，ＴｉＯ_２にフッ酸を加えたものや，ＨｆＯ_２をフッ酸に加えたものがある。これらを使用した場合，ＴｉＯ_２，ＨｆＯ_２の薄膜が容器表面に形成される。またその場合のイオン補足剤としては，ホウ酸が挙げられる。
【００１３】
前記成膜用溶液の容器の中への注入にあたっては注入管を用いると共に，該注入管の吐出口を前記容器内の底部近傍に位置させると，容器内の底部近傍から成膜用溶液を注入することができるので，容器内に対流を積極的に発生させて，溶液を均一化して容器表面に均一な成膜処理を施すことが可能である。
【００１４】
また容器内の溶液を排出するには，排出管を容器内の底部近傍まで挿入して排出すればよいが，たとえば容器自体を回転させるなどして，口を下方に向け，自重落下によって排出すれば，成膜の均一性を阻害するのを抑えることができる。なお排出管は，注入管と共用してもよい。
【００１５】
さらにまた，より排出の際の成膜の不均一性に与える影響を防止するには，前記所定時間経過後，前記成膜用溶液を容器の外へ排出する前に，前記容器内に成膜反応停止剤を注入すれば，その後の溶液の排出によっては，成膜された膜の均一性に影響がない。
たとえばフッ酸＋ＺｒＯ_２の溶液にホウ酸（ＢｒＯ_３）を加える例では，成膜反応停止剤としてフッ酸（ＨＦ）を注入すればよい。
【００１６】
成膜完了後，前記成膜用溶液を容器の外へ排出した後，フッ酸＋ＺｒＯ_２の溶液にホウ酸（ＢｒＯ_３）を加える例では，残留フッ酸が容器内に残り，そのままでは飲料用の容器として使用できない場合がある。したがって，適宜中和剤を注入して中和処理しても構わない。たとえばフッ酸＋ＺｒＯ_２の溶液にホウ酸（ＢｒＯ_３）を加える例では，適宜のアルカリ性溶液を容器内に注入してアルカリ処理することになる。
【００１７】
中和処理を行った後，水等でさらに洗浄することが好ましいが，この場合容器の中に飲用あるいは純水を供給することが好ましい。
【００１８】
また以上のような本発明の観点からすれば，たとえば容器の外側表面にも同様な方法で成膜処理することができる。
すなわち，成膜用溶液としての，希土類金属のフルオロ錯化合物及び金属フッ化物から選ばれた少なくとも１種の化合物の水溶液又は該化合物のフッ化水素酸溶液に，フッ化物イオン補足剤を加えたものに，そのまま容器を浸漬させ，所定時間経過後，容器を成膜用溶液から引き上げればよい。
【００１９】
本発明を実施する他の装置としては，たとえば容器内に成膜用溶液を注入するための注入管と，前記容器内の液体を容器の外に排出するための排出管とを有し，前記注入管の注入口及び排出管の吸込口を前記容器内に挿入させ，かつ前記注入管の注入口及び排出管の吸込口を前記容器内の底部近傍まで位置させるための移動機構とを有することを特徴とする，成膜装置が提案できる。なお排出管は，注入管とで共用し，適宜の切替によって注入管，排出管として機能させる構成であっても構わない。
【００２０】
排出管に代えて，容器を保持し，前記容器を回転させて前記容器の口を下方に向ける機能を有する管保持部材を有する構成とすれば，容器の口を下方に向けて自由落下による容器内の溶液の外部への排出を実行できる。
【００２１】
【発明の実施の形態】
以下，本発明の好ましい実施の形態について説明する。図１は，本発明にかかる成膜方法を実施するための成膜装置を有する注入，排出ラインの概要を示しており，成膜対象となるたとえばペットボトルなどの容器１は，保持部材２によって保持されている。
【００２２】
保持部材２は，容器１の外周を側方から把持自在であり，さらに保持部材２自体は適宜の駆動機構（図示せず）によって上下方向に昇降自在な支柱３によって指示されている。また支柱３自体は，適宜の駆動機構（図示せず）によって基台４上を水平方向に移動自在である。
【００２３】
基台４の上方には，第１の注入管１１，第１の排出管１２，第２の注入管１３，第２の排出管１４，第３の注入管１５，第３の排出管１６が，支柱３の移動方向に沿って配置されている。各注入管の吐出口１１ａ，１３ａ，１５ａ，各排出管の吸込口１２ａ，１４ａ，１６ａは，各々下方に向けられている。
【００２４】
第１の注入管１１は，ポンプ２１を介してタンク２２と接続されており，タンク２２内の成膜用溶液は，吐出口１１ａから吐出される。
第１の排出管１２は，ポンプ２３に接続され，吸込口１２ａから吸い込んだ液体を外部に排出するように構成されている。
【００２５】
第２の注入管１３は，ポンプ２５を介してタンク２６と接続されており，タンク２６内の中和剤が，吐出口１３ａから吐出される。
第２の排出管１４は，ポンプ２７に接続され，吸込口１４ａから吸い込んだ液体を外部に排出するように構成されている。なおかかる構成は，場合によっては，省略してもよい。
第３の注入管１５は，ポンプ２９を介してタンク３０と接続されており，タンク３０内の飲用水あるいは純水が，吐出口１５ａから吐出される。
第３の排出管１６は，ポンプ３１に接続され，吸込口１６ａから吸い込んだ液体を外部に排出するように構成されている。
なお必要に応じて，第３の注入管１５からの供給と第３の排出管１６からの排出プロセスは，繰り返し行ってもよい。
【００２６】
成膜装置の概要は以上に示したとおりであり，次に成膜方法の実施の形態について説明する。本実施の形態においては，タンク２２内の成膜用溶液として，酸化ジルコニウム１モル，フッ酸（ＨＦ）が０．６モル，Ｈ_２Ｏが６００モル，ホウ酸（ＢＯ_３Ｈ_３）が０．１モルの比率で混合された溶液を使用している。
【００２７】
そしてまず支柱３を移動させて保持部材２によって保持した容器１の口１ａを第１の注入管１１の真下に位置させる。次いで保持部材２を上昇させて，第１の注入管１１の吐出口１１ａを容器１内に挿入し，吐出口１１ａを容器１内の底部近傍にまで位置させる。その後ポンプ２１を作動させて，所定量の成膜用溶液を第１の注入管１１によって容器１の中に注入する。
このとき，酸化ジルコニウムのフッ化溶液の注入管と，ホウ酸の注入管とを別々に用意し，注入のタイミングをずらしてもよい。
【００２８】
次いで図３に示したように，保持部材２を下降させ，その後図４に示したように，支柱３を移動させて保持部材２によって保持した容器１の口１ａを第１の排出管１２の真下に位置させる。次いで図５に示したように，保持部材２を上昇させて，第１の排出管１２の吸込口１２ａを容器１内に挿入し，吸込口１２ａを容器１内の底部近傍にまで位置させる。その後ポンプ２３を稼働させて，容器１内の成膜用溶液を容器１の外に排出する。
【００２９】
成膜用溶液の容器１外への排出が完了すると，図６に示したように保持部材２を下降させ，次いで先の成膜用溶液の注入工程と同様にして，第２の注入管１３による容器１内への中和剤の注入，第２の排出管１４による中和剤の排出，第３の注入管１５による純水の注入，第３の排出管１６による純水の排出工程が順次行われる。
【００３０】
次に本実施の形態で使用した成膜用溶液による成膜について説明する。本実施の形態における成膜用溶液は，既述したように，ＺｒＯ_２が１モル，ＨＦが０．６モル，Ｈ_２Ｏが６００モルの比率で混合された金属フッ化物水溶液に，フッ化物イオン補足剤としてＢＯ_３Ｈ_３を０．１モル加えたものを使用している。
【００３１】
そして容器１内に当該成膜用溶液を注入して，容器１の内側表面と当該成膜用溶液との接触時間を，３〜１０秒とした。これによって，容器１の内側表面に，１０ｎｍ程度のＺｒＯ_２の薄膜が形成される。
【００３２】
したがって，従来のようにプラズマ成膜方法に拠らなくとも，容器１の内側表面に対して，容易にＺｒＯ_２の薄膜を形成することができる。
【００３３】
なお前記プロセスにおいて，成膜用溶液を容器１内に注入して所定時間経過の成膜用溶液の排出の時間管理が難しい場合には，排出する前に所定時間の終了後直ちに成膜反応を停止させることが便利である。そのため，所定時間経過直後，容器１内に直ちに成膜反応を停止させるための薬剤を注入することが好ましい。前記実施の形態を例にとると，ＨＦを容器１内に注入するとよい。ＨＦの注入にあたっては，前記した各注入管の構成と同様な注入管を用いて注入することができる。
【００３４】
前記実施の形態では容器１内の液体，たとえば成膜用溶液，中和剤，純水を容器１の外部に排出する際に，ポンプ，排出管を用いて吸引排液するようにしていたが，容器１の口１ａを下方に向けて自重落下によって容器１からこれらの液体を外部に排出するようにしてもよい。
【００３５】
そのためたとえば図７に示したように，保持部材２が容器１を保持したまま，回動するなどして容器１の上下を逆にするように，保持部材２に回転機能を持たせてもよい。そうすれば，図８に示したように，前記所定時間経過後，直ちに保持部材２を回転させて容器１の口１ａを下方に位置させ，そのまま自重によって容器１内の液体を容器１の外部に排出することができる。
【００３６】
その他中和剤，純水の容器１内への供給についても洗浄効果を高めるため，たとえば前記回転機能を有する保持部材２を用いて容器１の口を下方に向け，口１ａ内にこれら液体のノズルを下から挿入し，これらの液体を容器１内に向けて噴出するようにしてもよい。
【００３７】
なお前記実施の形態は，容器１の内側表面に成膜する方法であったが，本発明によれば，容器の外側に成膜することも可能である。かかる場合，たとえば成膜用溶液を貯留する槽内に，容器を浸漬させ，所定時間経過後に当該容器を槽から引き上げればよい。
【００３８】
【発明の効果】
本発明によれば，従来のようにプラズマＣＶＤによる成膜方法を採用しなくとも，たとえばペットボトルの内側表面に所定の薄膜，たとえば飲料用に供することができる酸化膜の薄膜を成膜することができ，従来プラズマＣＶＤ方法による各種の問題を解消して，安価でかつ多量に製品を提供できる。
【図面の簡単な説明】
【図１】本実施の形態において使用した保持部材を有する注入，排出ラインの説明図である。
【図２】図１の注入，排出ラインにおいて，容器内に成膜用溶液を注入している様子を示す説明図である。
【図３】図１の注入，排出ラインにおいて，溶液内への注入が完了した様子を示す説明図である。
【図４】図１の注入，排出ラインにおいて，第１の排出管の下に容器を移動させた様子を示す説明図である。
【図５】図１の注入，排出ラインにおいて，容器内の成膜用溶液を排出している様子を示す説明図である。
【図６】図１の注入，排出ラインにおいて，容器の成膜用溶液の排出が完了した様子を示す説明図である。
【図７】回転機能を有する保持部材によって容器を保持している状態を示す側面図である。
【図８】図７の保持容器を回転させて容器の口を下方に向けた状態を示す側面図である。
【符号の説明】
１容器
１ａ口
２保持部材
１１第１の注入管
１１ａ吐出口
１２第１の排出管
１２ａ吸込口[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method and an apparatus for forming a film on a surface of a container.
[0002]
[Prior art]
In recent years, plastic containers made of polyethylene terephthalate called PET bottles have been distributed in large quantities. However, when the beverage to be filled in the container is a high-temperature beverage, the oxidation of the beverage proceeds through the container, so that the inner surface of the container is Then, a DLC (Diamond Like Carbon) film or a Si-containing DLC film is formed by a plasma process.
[0003]
Conventionally, when the DLC film or the Si-containing DLC film is formed on the inner surface of a container such as a PET bottle, an outer electrode surrounding the container and an external electrode also serving as a decompression chamber is arranged outside the container. An internal electrode is disposed inside the container, a source gas is introduced into the container, a high frequency is applied to the external electrode to generate plasma in the container, and a predetermined film forming process is performed on the inner surface of the container. A plasma CVD method is employed (for example, see Patent Document 1).
[0004]
[Patent Document 1]
JP 2001-335946 A
[Problems to be solved by the invention]
However, in the above-mentioned conventional method, the apparatus itself for carrying out the method is complicated, a vacuum pump and a matching box for matching must be prepared, and the shape is different depending on the outer shape of the container. External electrodes also had to be prepared separately. Further, it takes time to reach a predetermined degree of pressure reduction, and the production per unit time is not satisfactory. In addition, since the surface of the internal electrode disposed in the container is also formed, it is complicated to periodically clean the internal electrode. Furthermore, due to the structure of the external electrode, the applicable shape of the container has been limited.
[0006]
SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and when forming a film on the surface of a container such as the above-mentioned PET bottle, it is easy to handle without using such a plasma CVD method. It is an object of the present invention to provide a highly reliable film forming method and an apparatus therefor.
[0007]
[Means for Solving the Problems]
In order to achieve the above object, the present invention relates to a film forming method for forming a film on an inner surface of a container, wherein a rare earth metal fluoro complex compound as a film forming solution is provided in the container to be formed. And an aqueous solution of at least one compound selected from metal fluorides or a hydrofluoric acid solution of the compound is injected to bring the inner surface of the container into contact with the solution for film formation. The solution is discharged outside the container.
[0008]
According to the present invention, an aqueous solution of at least one compound selected from a fluoro complex compound of a rare earth metal and a metal fluoride, or a solution obtained by adding a fluoride ion scavenger to a hydrofluoric acid solution of the compound in a container Are injected to bring the inner periphery of the container into contact with the solution for film formation, so that oxides in these aqueous solutions precipitate on the inner surface of the container to form a thin film.
[0009]
For example, when a solution obtained by adding boric acid (BrO ₃ ) to a solution of hydrofluoric acid and ZrO ₂ is used, a thin film of ZrO ₂ is formed on the inner surface of the container.
The chemical equilibrium is as shown in equations (1) and (2). The specific reaction process is described in detail in Ken Yagi, "Synthesis of functional ceramic materials from aqueous solutions" (J Mater. Res. Vol. 13 No. 5 May 1998).
[0010]
(Equation 1)

[0011]
Therefore, a thin film of these oxides can be formed on the inner surface of the container without using a conventional film forming method by plasma CVD.
[0012]
Examples of the aqueous solution of at least one compound selected from the group consisting of a fluorocarbon complex compound of a rare earth metal and a metal fluoride as a solution for film formation suitable for the present invention include, for example, a solution obtained by adding hydrofluoric acid to TiO ₂ or HfO _2. Is added to hydrofluoric acid. When these are used, a thin film of TiO ₂ and HfO ₂ is formed on the surface of the container. In this case, boric acid may be used as an ion scavenger.
[0013]
When the film-forming solution is injected into the container, an injection tube is used, and when the discharge port of the injection tube is positioned near the bottom in the container, the film-forming solution is injected from near the bottom in the container. Therefore, convection can be positively generated in the container, the solution can be made uniform, and a uniform film forming process can be performed on the surface of the container.
[0014]
In order to discharge the solution in the container, it is sufficient to insert the discharge pipe to the vicinity of the bottom of the container and discharge it. However, for example, by rotating the container itself, turning the mouth downward and discharging by gravity. For example, it is possible to prevent the uniformity of film formation from being hindered. The discharge pipe may be shared with the injection pipe.
[0015]
Furthermore, in order to prevent the influence on the non-uniformity of the film formation at the time of discharging, the film is formed in the container after the predetermined time has elapsed and before the film forming solution is discharged out of the container. If the reaction terminator is injected, the uniformity of the formed film is not affected by the subsequent discharge of the solution.
For example, in the case of adding boric acid (BrO ₃ ) to a solution of hydrofluoric acid + ZrO ₂ , hydrofluoric acid (HF) may be injected as a film formation reaction stopping agent.
[0016]
In the example where boric acid (BrO ₃ ) is added to the solution of hydrofluoric acid + ZrO ₂ after the film forming solution is discharged out of the container after the film formation is completed, the residual hydrofluoric acid remains in the container, and as it is for beverages. May not be used as a container. Therefore, the neutralizing treatment may be performed by appropriately injecting a neutralizing agent. For example, in the case of adding boric acid (BrO ₃ ) to a solution of hydrofluoric acid + ZrO ₂ , an appropriate alkaline solution is injected into a container and alkali treatment is performed.
[0017]
After the neutralization treatment, it is preferable to further wash with water or the like. In this case, it is preferable to supply drinking water or pure water into the container.
[0018]
Further, from the viewpoint of the present invention as described above, for example, a film can be formed on the outer surface of the container by the same method.
That is, an aqueous solution of at least one compound selected from a fluoro complex compound of a rare earth metal and a metal fluoride or a hydrofluoric acid solution of the compound and a fluoride ion scavenger added as a solution for film formation. Then, the container may be immersed as it is, and after a lapse of a predetermined time, the container may be pulled out of the solution for film formation.
[0019]
Another apparatus for carrying out the present invention includes, for example, an injection pipe for injecting a film forming solution into a container, and a discharge pipe for discharging the liquid in the container out of the container. A moving mechanism for inserting the inlet of the injection pipe and the inlet of the discharge pipe into the container, and positioning the inlet of the injection pipe and the suction port of the discharge pipe near the bottom of the container; A film forming apparatus characterized by the following can be proposed. Note that the discharge pipe may be shared with the injection pipe, and may be configured to function as the injection pipe and the discharge pipe by appropriate switching.
[0020]
A container having a function of holding the container and having a function of rotating the container and directing the mouth of the container downward instead of the discharge pipe may be configured such that the container is free-falling with the mouth of the container facing downward. Draining of the solution inside can be performed.
[0021]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, preferred embodiments of the present invention will be described. FIG. 1 shows an outline of an injection / discharge line having a film forming apparatus for performing a film forming method according to the present invention. Is held.
[0022]
The holding member 2 is capable of gripping the outer periphery of the container 1 from the side, and the holding member 2 itself is indicated by a column 3 which can be moved up and down by an appropriate driving mechanism (not shown). The support 3 itself is horizontally movable on the base 4 by an appropriate drive mechanism (not shown).
[0023]
Above the base 4, a first injection pipe 11, a first discharge pipe 12, a second injection pipe 13, a second discharge pipe 14, a third injection pipe 15, and a third discharge pipe 16 are provided. , Are arranged along the moving direction of the column 3. The

discharge ports

11a, 13a, 15a of each injection pipe and the

suction ports

12a, 14a, 16a of each discharge pipe are directed downward.
[0024]
The first injection pipe 11 is connected to a tank 22 via a pump 21, and the film forming solution in the tank 22 is discharged from a discharge port 11a.
The first discharge pipe 12 is connected to a pump 23, and is configured to discharge the liquid sucked from the suction port 12a to the outside.
[0025]
The second injection pipe 13 is connected to a tank 26 via a pump 25, and the neutralizing agent in the tank 26 is discharged from a discharge port 13a.
The second discharge pipe 14 is connected to the pump 27 and configured to discharge the liquid sucked from the suction port 14a to the outside. Such a configuration may be omitted in some cases.
The third injection pipe 15 is connected to the tank 30 via the pump 29, and the drinking water or pure water in the tank 30 is discharged from the discharge port 15a.
The third discharge pipe 16 is connected to the pump 31 and is configured to discharge the liquid sucked from the suction port 16a to the outside.
Note that the supply process from the third injection pipe 15 and the discharge process from the third discharge pipe 16 may be repeatedly performed as necessary.
[0026]
The outline of the film forming apparatus is as described above. Next, an embodiment of the film forming method will be described. In the present embodiment, as a film forming solution in the

tank

22, 1 mol of zirconium oxide, 0.6 mol of hydrofluoric acid (HF), 600 mol of H ₂ O, and 0 mol of boric acid (BO ₃ H ₃ ) are used. A solution mixed in a .1 molar ratio is used.
[0027]
Then, first, the column 3 is moved so that the mouth 1 a of the container 1 held by the holding member 2 is positioned directly below the first injection pipe 11. Next, the holding member 2 is raised, and the discharge port 11a of the first injection pipe 11 is inserted into the container 1 so that the discharge port 11a is positioned near the bottom of the container 1. Thereafter, the pump 21 is operated, and a predetermined amount of the film forming solution is injected into the container 1 through the first injection pipe 11.
At this time, the injection pipe for the fluorinated solution of zirconium oxide and the injection pipe for boric acid may be separately prepared, and the injection timing may be shifted.
[0028]
Next, as shown in FIG. 3, the holding member 2 is lowered, and then, as shown in FIG. 4, the post 3 a is moved to move the opening 1 a of the container 1 held by the holding member 2 into the first discharge pipe 12. Position it directly below. Next, as shown in FIG. 5, the holding member 2 is raised, and the suction port 12a of the first discharge pipe 12 is inserted into the container 1, and the suction port 12a is positioned near the bottom of the container 1. After that, the pump 23 is operated to discharge the solution for film formation in the container 1 out of the container 1.
[0029]
When the film-forming solution is completely discharged from the container 1, the holding member 2 is lowered as shown in FIG. 6, and then the second injection pipe 13 is formed in the same manner as in the film-forming solution injection step. Of the neutralizing agent into the container 1 by the above, discharge of the neutralizing agent by the second discharge pipe 14, injection of the pure water by the third injection pipe 15, and discharge of the pure water by the third discharge pipe 16. It is performed sequentially.
[0030]
Next, film formation using the film formation solution used in this embodiment will be described. As described above, the film-forming solution according to the present embodiment is obtained by mixing a metal fluoride aqueous solution in which 1 mol of ZrO ₂ , 0.6 mol of HF, and 600 mol of H ₂ O are mixed with each other. As the ion scavenger, one added with 0.1 mol of BO ₃ H ₃ is used.
[0031]
Then, the film forming solution was poured into the container 1, and the contact time between the inner surface of the container 1 and the film forming solution was set to 3 to 10 seconds. As a result, a thin film of ZrO ₂ of about 10 nm is formed on the inner surface of the container 1.
[0032]
Therefore, a ZrO ₂ thin film can be easily formed on the inner surface of the container 1 without depending on the plasma film forming method as in the related art.
[0033]
In the above process, when it is difficult to control the time for discharging the film-forming solution after a predetermined time has elapsed after the film-forming solution is injected into the container 1, the film-forming reaction is performed immediately after the predetermined time has elapsed before the film-forming solution is discharged. It is convenient to stop. Therefore, it is preferable to immediately inject a chemical for stopping the film forming reaction into the container 1 immediately after the elapse of the predetermined time. Taking the above embodiment as an example, HF may be injected into the container 1. When injecting HF, the injection can be performed using the same injection tube as the above-described injection tube.
[0034]
In the above-described embodiment, when the liquid in the container 1, for example, a film forming solution, a neutralizing agent, and pure water is discharged to the outside of the container 1, suction and discharge are performed using a pump and a discharge pipe. Alternatively, these liquids may be discharged from the container 1 to the outside by falling under its own weight with the mouth 1a of the container 1 facing downward.
[0035]
Therefore, as shown in FIG. 7, for example, the holding member 2 may be provided with a rotation function such that the holding member 2 rotates while holding the container 1 so that the container 1 is turned upside down. . Then, as shown in FIG. 8, after the lapse of the predetermined time, the holding member 2 is immediately rotated to position the mouth 1a of the container 1 below, and the liquid in the container 1 is removed from the container 1 by its own weight. Can be discharged.
[0036]
In addition, in order to enhance the cleaning effect also with respect to the supply of the neutralizing agent and pure water into the container 1, for example, the mouth of the container 1 is turned downward by using the holding member 2 having the rotating function, and these liquids are introduced into the mouth 1a. A nozzle may be inserted from below to eject these liquids into the container 1.
[0037]
In the above embodiment, the film is formed on the inner surface of the container 1. However, according to the present invention, the film can be formed on the outer surface of the container. In such a case, for example, the container may be immersed in a tank for storing a film-forming solution, and the container may be lifted from the tank after a predetermined time has elapsed.
[0038]
【The invention's effect】
According to the present invention, a predetermined thin film, for example, an oxide thin film that can be used for beverages is formed on the inner surface of a PET bottle without employing a film forming method by plasma CVD as in the related art. Thus, various problems caused by the conventional plasma CVD method can be solved, and a large number of products can be provided at low cost.
[Brief description of the drawings]
FIG. 1 is an explanatory diagram of an injection / discharge line having a holding member used in the present embodiment.
FIG. 2 is an explanatory view showing a state in which a film-forming solution is injected into a container in the injection and discharge lines in FIG.
FIG. 3 is an explanatory view showing a state in which the injection into the solution is completed in the injection and discharge lines in FIG. 1;
FIG. 4 is an explanatory view showing a state in which a container is moved below a first discharge pipe in the injection / discharge line of FIG. 1;
FIG. 5 is an explanatory view showing a state in which a film-forming solution in a container is being discharged in an injection / discharge line of FIG. 1;
FIG. 6 is an explanatory diagram showing a state in which the discharge of the film-forming solution from the container is completed in the injection / discharge line of FIG. 1;
FIG. 7 is a side view showing a state where the container is held by a holding member having a rotating function.
8 is a side view showing a state in which the holding container of FIG. 7 is rotated and the mouth of the container is directed downward.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Container 1a Port 2 Holding member 11 First injection pipe 11a Discharge port 12 First discharge pipe 12a Suction port

Claims

A film forming method for forming a film on an inner surface of a container,
In the container,
An aqueous solution of at least one compound selected from a fluoro complex compound of a rare earth metal and a metal fluoride, or a solution obtained by adding a fluoride ion scavenger to a hydrofluoric acid solution of the compound,
And contact the inner surface of the container with the film forming solution,
A film forming method, characterized in that after a predetermined time has elapsed, the film forming solution is discharged out of a container.

2. The film-forming method according to claim 1, wherein an injection tube is used for injecting the film-forming solution into the container, and an outlet of the injection tube is located near a bottom in the container. Method.

3. The method according to claim 1, wherein, when discharging the film-forming solution to the outside of the container, the film-forming solution is discharged by dropping its own weight with the opening of the container facing downward. Membrane method.

4. The composition according to claim 1, wherein after the predetermined time has elapsed, before the solution for film formation is discharged out of the container, a film-forming reaction terminator is injected into the container. Membrane method.

After discharging the film-forming solution out of the container,
5. The film forming method according to claim 1, further comprising a step of supplying drinking water or pure water into the container to wash the inside of the container.

A film forming method for forming a film on an outer surface of a container,
The container for film formation is
An aqueous solution of at least one compound selected from a fluoro complex compound of a rare earth metal and a metal fluoride as a solution for film formation, or a solution obtained by adding a fluoride ion scavenger to a hydrofluoric acid solution of the compound,
And dipping the container from the film forming solution after a predetermined time has elapsed.

An apparatus for forming a coating on the inner peripheral surface of a container,
An injection tube for injecting a film-forming solution into the container,
A discharge pipe for discharging the liquid in the container out of the container,
A moving mechanism for inserting the inlet of the injection pipe and the inlet of the discharge pipe into the container, and positioning the inlet of the injection pipe and the suction of the discharge pipe near the bottom in the container; A film forming apparatus, characterized in that:

An apparatus for forming a coating on the inner peripheral surface of a container,
An injection tube for injecting a liquid into the container;
A moving mechanism for inserting the injection port of the injection pipe into the container, and positioning the injection port of the injection pipe to near the bottom of the container;
A tube holding member having a function of holding the container, rotating the container, and turning the mouth of the container downward;
A film forming apparatus, comprising: