JP2009178956A - Transparent gas barrier film and its use - Google Patents
Transparent gas barrier film and its use Download PDFInfo
- Publication number
- JP2009178956A JP2009178956A JP2008020578A JP2008020578A JP2009178956A JP 2009178956 A JP2009178956 A JP 2009178956A JP 2008020578 A JP2008020578 A JP 2008020578A JP 2008020578 A JP2008020578 A JP 2008020578A JP 2009178956 A JP2009178956 A JP 2009178956A
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- Prior art keywords
- film
- gas barrier
- plasma
- barrier film
- transparent
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- 239000006078 metal deactivator Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical class C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- AODWRBPUCXIRKB-UHFFFAOYSA-N naphthalene perylene Chemical group C1=CC=CC2=CC=CC=C21.C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 AODWRBPUCXIRKB-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical class C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Chemical class 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920000548 poly(silane) polymer Chemical class 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical class O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- 150000005255 pyrrolopyridines Chemical class 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical class C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- XBFJAVXCNXDMBH-UHFFFAOYSA-N tetracyclo[6.2.1.1(3,6).0(2,7)]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1 XBFJAVXCNXDMBH-UHFFFAOYSA-N 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- QKTRRACPJVYJNU-UHFFFAOYSA-N thiadiazolo[5,4-b]pyridine Chemical class C1=CN=C2SN=NC2=C1 QKTRRACPJVYJNU-UHFFFAOYSA-N 0.000 description 1
- NZFNXWQNBYZDAQ-UHFFFAOYSA-N thioridazine hydrochloride Chemical class Cl.C12=CC(SC)=CC=C2SC2=CC=CC=C2N1CCC1CCCCN1C NZFNXWQNBYZDAQ-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Landscapes
- Electroluminescent Light Sources (AREA)
- Laminated Bodies (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
本発明は、透明ガスバリア性フィルムに関し、さらに詳しくは、少なくとも片面に少なくとも一層の無機膜を有してなる、水蒸気バリア性、透明性及び寸法安定性に優れる透明ガスバリア性フィルムに関する。 The present invention relates to a transparent gas barrier film, and more particularly, to a transparent gas barrier film having at least one inorganic film on at least one surface and excellent in water vapor barrier property, transparency and dimensional stability.
従来、プラスチック基板やフィルムの表面に酸化アルミニウム、酸化マグネシウム、酸化珪素等の金属酸化物の薄膜を形成したガスバリア性フィルムは、酸素や水蒸気の遮断を必要とする物品の包装、食品や工業用品および医薬品等の変質を防止するための包装用途に多く用いられている。また、包装用途以外にも、液晶表示素子、太陽電池、エレクトロルミネッセンス（ＥＬ）基板等での使用が検討されている。特に、液晶表示素子やＥＬ素子等への応用が進んでいる透明基材に関しては、軽量化、大型化という要求に加え、長期信頼性や形状の自由度が高いこと、曲面表示が可能であること等の高度な要求が加わり、重くて割れやすく大面積化が困難なガラス基板に代わって透明プラスチック等のフィルム基材が注目されており、液晶表示素子においては一部採用され始めている。また、プラスチックフィルムは上記要求に応えるだけでなく、ロール・トゥ・ロール方式が可能であることから、ガラス基板よりも生産性が良く、コストダウンの点でも有利である。 Conventionally, a gas barrier film in which a metal oxide thin film such as aluminum oxide, magnesium oxide, silicon oxide or the like is formed on the surface of a plastic substrate or film is used for wrapping articles, foods, industrial products and the like that need to block oxygen and water vapor. It is often used in packaging applications to prevent alteration of pharmaceuticals. In addition to packaging applications, use in liquid crystal display elements, solar cells, electroluminescence (EL) substrates and the like has been studied. In particular, for transparent substrates that are being applied to liquid crystal display elements, EL elements, etc., in addition to demands for weight reduction and size increase, long-term reliability and high degree of freedom of shape are possible, and curved surface display is possible. In response to such high demands, film base materials such as transparent plastics have attracted attention in place of glass substrates that are heavy, easily broken, and difficult to increase in area, and some of them have begun to be used in liquid crystal display elements. In addition, the plastic film not only meets the above requirements, but also can be rolled-to-roll, so it has better productivity than a glass substrate and is advantageous in terms of cost reduction.
しかしながら、透明プラスチック等のフィルム基板は、ガラス基板に対してガスバリア性が劣るという問題がある。このようなガスバリア性に劣る基材を上記の用途に用いると、ガスが浸透して問題が生じる。例えば液晶セル内の液晶が劣化したり、有機ＥＬ素子が劣化したりして、表示欠陥となって表示品位が劣化する。 However, a film substrate such as a transparent plastic has a problem that gas barrier properties are inferior to a glass substrate. When such a base material having inferior gas barrier properties is used for the above-mentioned applications, gas permeates and causes a problem. For example, the liquid crystal in the liquid crystal cell deteriorates or the organic EL element deteriorates, resulting in a display defect and display quality.
このような問題を解決するために、フィルム基板上に金属酸化物薄膜を形成してガスバリア性フィルム基材とすることが知られている。包装部材や液晶表示素子に使用されるガスバリアフィルムとしては、樹脂フィルム上にガスバリア無機質層として窒素を含む酸化珪素膜、無機質層として炭素を含む酸化珪素膜が積層されてなるガスバリアフィルム基板（特許文献１）が知られている。また、基材フィルムに無機酸化物層と、酸化窒化炭化珪素層もしくは酸化炭化珪素層をこの順に有するガスバリア性積層体（特許文献２）が知られている。また、透明プラスチックフィルムに窒化珪素膜が成膜されている透明バリアフィルム（特許文献３）が知られている。しかしながら、使用環境により、そりなどが生じる問題が発生していた。 In order to solve such problems, it is known to form a metal oxide thin film on a film substrate to form a gas barrier film substrate. As a gas barrier film used for a packaging member and a liquid crystal display element, a gas barrier film substrate in which a silicon oxide film containing nitrogen as a gas barrier inorganic layer and a silicon oxide film containing carbon as an inorganic layer are laminated on a resin film (Patent Document) 1) is known. Further, a gas barrier laminate (Patent Document 2) having an inorganic oxide layer and a silicon oxynitride carbide layer or a silicon oxide carbide layer in this order on a base film is known. Further, a transparent barrier film (Patent Document 3) in which a silicon nitride film is formed on a transparent plastic film is known. However, there has been a problem of warping depending on the use environment.
一方、無機膜との界面において剥離や剥離に伴う欠陥が生じにくく、密着性が高くかつ脱ガスが低い有機膜を用いたガスバリア積層体が知られている（特許文献４）。しかしながら、より高いガスバリア性を必要とする用途に使用される場合には、未だ不充分なものであった。 On the other hand, there has been known a gas barrier laminate using an organic film which is less likely to cause peeling and a defect accompanying peeling at the interface with the inorganic film, has high adhesion, and has low degassing (Patent Document 4). However, it was still insufficient when used for applications requiring higher gas barrier properties.
プラスチックフィルム上に無機薄膜等を成膜する方法としては、高周波によるイオンプレーティング法、又はホローカソードガンを用いたイオンプレーティング法、プラズマ発生装置を用いたイオンビームミキシング法、シートプラズマ法が知られている。（例えば、特許文献５参照）しかしながら、上記方法で成膜したフィルム基板は光学素子として使用する場合には、全光線透過率が不充分なものであった。 As a method for forming an inorganic thin film on a plastic film, a high-frequency ion plating method, an ion plating method using a hollow cathode gun, an ion beam mixing method using a plasma generator, or a sheet plasma method is known. It has been. However, when used as an optical element, the film substrate formed by the above method has an insufficient total light transmittance.
本発明の目的は、透明性が高く、寸法安定性に優れ、高い水蒸気バリア性を有するフィルムを形成することである。 An object of the present invention is to form a film having high transparency, excellent dimensional stability, and high water vapor barrier properties.
本発明者は、上記目的を達成すべく鋭意研究を重ねた結果、透明プラスチックフィルムの少なくとも片面に少なくとも一層の無機膜を有する透明ガスバリア性フィルムであって、該無機膜が、特定の装置を用いたスパッタイオンプレーティング法によって無機膜を形成することにより、上記目的を達成し得ることを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the present inventor is a transparent gas barrier film having at least one inorganic film on at least one surface of a transparent plastic film, and the inorganic film uses a specific device. The present inventors have found that the above object can be achieved by forming an inorganic film by the conventional sputtering ion plating method, and have completed the present invention.
かくして本発明によれば、以下（１）〜（７）が提供される。
（１）透明プラスチックフィルムの少なくとも片面に少なくとも一層の無機膜を有する透明ガスバリア性フィルムであって、該無機膜が、
プラズマの輸送方向の中心に対して略等密度分布するソースプラズマを放電により形成して、前記ソースプラズマを前記輸送方向に向けて放出可能なプラズマガンと、
前記輸送方向に延びた輸送空間を有するシートプラズマ変形室と、
互いに同極同士を向き合わせて、前記輸送空間を挟むように配置される第１の磁界発生手段の対と、
前記輸送空間に連通した成膜空間を有する成膜室と、
互いに異極同士を向き合わせて、前記成膜空間を挟むように配置される第２の磁界発生手段の対と、を備え、
前記ソースプラズマは、前記輸送空間を移動する間に、前記第１の磁界発生手段の対の磁界により前記中心を含む主面に沿ってシート状に拡がり、
前記シート状のプラズマは、前記成膜空間を移動する間に、前記第２の磁界発生手段の対の磁界により前記主面から凸状に偏倚する装置を用いたスパッタイオンプレーティング法によって形成されることを特徴とする透明ガスバリア性フィルム。
（２）前記透明プラスチックフィルムが、１２０℃以上のガラス転移温度を有する高分子材料で形成されている前記（１）記載の透明ガスバリア性フィルム。
（３）前記無機膜が酸化珪素、酸化窒化珪素及び窒化珪素のいずれかからなるものであることを特徴とする前記（１）または（２）記載の透明ガスバリア性フィルム。
（４）前記透明プラスチックフィルムが、０．０５重量％以下の吸水率を有する高分子材料で形成されている前記（１）〜（３）のいずれかに記載の透明ガスバリア性フィルム。
（５）前記透明プラスチックフィルムが、環状オレフィンポリマーを成分として形成される前記（１）〜（４）のいずれかに記載の透明ガスバリア性フィルム。
（６）前記（１）〜（５）のいずれかに記載の透明ガスバリアフィルムを用いた光学素子。
（７）前記（１）〜（５）のいずれかに記載の透明ガスバリアフィルムを用いた有機エレクトロルミネッセンス素子。
Thus, according to the present invention, the following (1) to (7) are provided.
(1) A transparent gas barrier film having at least one inorganic film on at least one side of a transparent plastic film, the inorganic film being
A plasma gun capable of forming a source plasma having a substantially equal density distribution with respect to the center in the transport direction of the plasma by discharge, and discharging the source plasma in the transport direction;
A sheet plasma deformation chamber having a transport space extending in the transport direction;
A pair of first magnetic field generating means arranged to face each other with the same polarity and sandwich the transport space;
A film formation chamber having a film formation space communicating with the transport space;
A pair of second magnetic field generating means arranged so as to face each other different polarities and sandwich the film formation space,
The source plasma spreads in a sheet shape along the main surface including the center by the magnetic field of the pair of the first magnetic field generating means while moving in the transport space,
The sheet-like plasma is formed by a sputter ion plating method using an apparatus that is biased from the main surface by the magnetic field of the pair of the second magnetic field generating means while moving in the film formation space. A transparent gas barrier film characterized by the above.
(2) The transparent gas barrier film according to (1), wherein the transparent plastic film is formed of a polymer material having a glass transition temperature of 120 ° C. or higher.
(3) The transparent gas barrier film according to (1) or (2), wherein the inorganic film is made of any one of silicon oxide, silicon oxynitride, and silicon nitride.
(4) The transparent gas barrier film according to any one of (1) to (3), wherein the transparent plastic film is formed of a polymer material having a water absorption rate of 0.05% by weight or less.
(5) The transparent gas barrier film according to any one of (1) to (4), wherein the transparent plastic film is formed using a cyclic olefin polymer as a component.
(6) An optical element using the transparent gas barrier film according to any one of (1) to (5).
(7) The organic electroluminescent element using the transparent gas barrier film in any one of said (1)-(5).
本発明の透明ガスバリア性フィルムは、透明性が高く、寸法安定性に優れ、高い水蒸気バリア性を有するフィルムである。
このフィルムは、内容物の品質を変化させる原因となる水蒸気をほとんど透過させないので、高いガスバリア性が要求される用途、例えば食品や医薬品等の包装材料やパッケージ材料、有機エレクトロルミネッセンス表示素子や液晶表示素子などの光学素子等に好ましく用いることができる。
The transparent gas barrier film of the present invention is a film having high transparency, excellent dimensional stability, and high water vapor barrier properties.
This film hardly permeates water vapor that causes the quality of the contents to change, so applications that require high gas barrier properties such as packaging materials and packaging materials such as food and pharmaceuticals, organic electroluminescence display elements and liquid crystal displays It can be preferably used for an optical element such as an element.
本発明の透明プラスチックフィルムは、少なくとも片面に少なくとも一層の無機膜を有する透明ガスバリア性フィルムであって、該無機膜が、プラズマの輸送方向の中心に対して略等密度分布するソースプラズマを放電により形成して、前記ソースプラズマを前記輸送方向に向けて放出可能なプラズマガンと、前記輸送方向に延びた輸送空間を有するシートプラズマ変形室と、互いに同極同士を向き合わせて、前記輸送空間を挟むように配置される第１の磁界発生手段の対と、前記輸送空間に連通した成膜空間を有する成膜室と、互いに異極同士を向き合わせて、前記成膜空間を挟むように配置される第２の磁界発生手段の対と、を備え、前記ソースプラズマは、前記輸送空間を移動する間に、前記第１の磁界発生手段の対の磁界により前記中心を含む主面に沿ってシート状に拡がり、前記シート状のプラズマは、前記成膜空間を移動する間に、前記第２の磁界発生手段の対の磁界により前記主面から凸状に偏倚する装置を用いたスパッタイオンプレーティング法によって形成されることを特徴とする。 The transparent plastic film of the present invention is a transparent gas barrier film having at least one inorganic film on at least one side, and the inorganic film is discharged by discharging a source plasma having a substantially equal density distribution with respect to the center in the plasma transport direction. Forming a plasma gun capable of emitting the source plasma in the transport direction, a sheet plasma deformation chamber having a transport space extending in the transport direction, and facing the same polarity to each other, thereby forming the transport space A pair of first magnetic field generating means arranged so as to be sandwiched, a film forming chamber having a film forming space communicating with the transport space, and facing each other with different polarities and arranged so as to sandwich the film forming space A pair of second magnetic field generating means, wherein the source plasma is moved by the magnetic field of the pair of first magnetic field generating means while moving in the transport space. The sheet-shaped plasma spreads in a sheet shape along the main surface including the center, and the sheet-shaped plasma is biased in a convex shape from the main surface by the magnetic field of the pair of the second magnetic field generating means while moving in the film formation space. It is characterized by being formed by a sputter ion plating method using an apparatus that performs the above.
本発明の透明プラスチックフィルムを構成する材料、及びその形成方法について説明する。 The material which comprises the transparent plastic film of this invention, and its formation method are demonstrated.
（透明プラスチックフィルム）
本発明の透明ガスバリア性フィルムを構成する透明プラスチックフィルム（以下、基材フィルムという）は、透明樹脂を成形して得られるものである。
透明樹脂としては、その利用される分野の要求性能に従い、適宜選択すればよい。光学素子に要求される性能は、耐熱性、光学特性等であり、従って、この用途に適した基材フィルムの樹脂としては、ポリ（メタ）アクリレート、ポリ（メタ）アリレート（ＰＡＲ）、ポリイミド（ＰＩ）、ポリアミドイミド（ＰＡＩ）、ポリエーテルサルホン（ＰＥＳ）、ポリエチレンナフタレート（ＰＥＮ）ポリカーボネート（ＰＣ）、環状オレフィンポリマー、ポリシクロヘキセン、ポリエーテルケトン（ＰＥＫ）、ポリエーテルエーテルケトン（ＰＥＥＫ）、ポリエーテルイミド（ＰＥＩ）、ポリシロキサン系、エチレン−四フッ化エチレン共重合体（ＥＴＦＥ）、三フッ化塩化エチレン（ＰＦＡ）、四フッ化エチレン−パーフルオロアルキルビニルエーテル共重合体（ＦＥＰ）、フッ化ビニリデン（ＰＶＤＦ）、フッ化ビニル（ＰＶＦ）、パーフルオロエチレン−パーフロロプロピレン−パーフロロビニルエーテル−共重合体（ＥＰＡ）等のフッ素系樹脂等を挙げることができる。耐熱性、寸法安定性、吸水率及び低水蒸気透過性の観点から、基材フィルムとして用いる樹脂としては環状オレフィンポリマーが好ましい。例えば、ＰＥＳ、ＰＥＮなどの吸水率の高い樹脂を基材フィルムとして用いた場合、恒温恒湿条件下で反りなどが発生するおそれがある。
(Transparent plastic film)
The transparent plastic film (hereinafter referred to as a base film) constituting the transparent gas barrier film of the present invention is obtained by molding a transparent resin.
The transparent resin may be appropriately selected according to the required performance in the field in which it is used. The performance required for the optical element is heat resistance, optical characteristics, etc. Therefore, as the resin of the base film suitable for this application, poly (meth) acrylate, poly (meth) arylate (PAR), polyimide ( PI), polyamideimide (PAI), polyethersulfone (PES), polyethylene naphthalate (PEN) polycarbonate (PC), cyclic olefin polymer, polycyclohexene, polyetherketone (PEK), polyetheretherketone (PEEK), Polyetherimide (PEI), polysiloxane, ethylene-tetrafluoroethylene copolymer (ETFE), ethylene trifluoride chloride (PFA), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (FEP), fluorine Vinylidene fluoride (PVDF), vinyl fluoride (P F), perfluoro ethylene - perfluoro propylene - perfluoro ether - can be exemplified a fluorine-based resin such as copolymer (EPA). From the viewpoints of heat resistance, dimensional stability, water absorption, and low water vapor permeability, a cyclic olefin polymer is preferable as the resin used as the base film. For example, when a resin having a high water absorption rate such as PES or PEN is used as the base film, warping or the like may occur under constant temperature and humidity conditions.
本発明の基材フィルム材料として好適な環状オレフィンポリマーについて、以下に詳述する。
本発明で用いる環状オレフィンポリマーは、脂環式構造を含有してなる繰り返し単位を有する重合体である。環状オレフィンポリマー中の脂環式構造としては、飽和環状炭化水素（シクロアルカン）構造、不飽和環状炭化水素（シクロアルケン）構造などが挙げられるが、機械強度、耐熱性などの観点から、シクロアルカン構造やシクロアルケン構造が好ましく、中でもシクロアルカン構造が最も好ましい。脂環式構造は主鎖にあっても良いし、側鎖にあっても良いが、機械強度、耐熱性などの観点から、主鎖に脂環式構造を含有するものが好ましい。脂環式構造を構成する炭素原子数には、格別な制限はないが、通常４〜３０個、好ましくは５〜２０個、より好ましくは５〜１５個の範囲であるときに、機械強度、耐熱性、及びフィルムの成形性の特性が高度にバランスされる。
The cyclic olefin polymer suitable as the base film material of the present invention is described in detail below.
The cyclic olefin polymer used in the present invention is a polymer having a repeating unit containing an alicyclic structure. Examples of the alicyclic structure in the cyclic olefin polymer include a saturated cyclic hydrocarbon (cycloalkane) structure and an unsaturated cyclic hydrocarbon (cycloalkene) structure. From the viewpoint of mechanical strength and heat resistance, cycloalkane. A structure or a cycloalkene structure is preferable, and a cycloalkane structure is most preferable. The alicyclic structure may be in the main chain or in the side chain, but those containing an alicyclic structure in the main chain are preferred from the viewpoint of mechanical strength, heat resistance and the like. The number of carbon atoms constituting the alicyclic structure is not particularly limited, but is usually 4 to 30, preferably 5 to 20, more preferably 5 to 15 in the mechanical strength, The properties of heat resistance and film formability are highly balanced.
環状オレフィンポリマー中の脂環式構造を含有してなる繰り返し単位の割合は、使用目的に応じて適宜選択されればよいが、好ましくは５０重量％以上、さらに好ましくは７０重量％以上、特に好ましくは９０重量％以上である。脂環式構造含有重合体中の脂環式構造を含有してなる繰り返し単位の割合がこの範囲にあるとフィルムの透明性および耐熱性の観点から好ましい。
この環状オレフィンポリマーの具体例としては、（１）ノルボルネン系重合体、（２）単環の環状オレフィン系重合体、（３）環状共役ジエン系重合体、（４）ビニル脂環式炭化水素系重合体、及び（１）〜（４）の水素化物などが挙げられる。これらの中でも、耐熱性、機械的強度等の観点から、ノルボルネン系重合体の水素化物、ビニル脂環式炭化水素重合体及びその水素化物が好ましい。
The proportion of the repeating unit containing an alicyclic structure in the cyclic olefin polymer may be appropriately selected depending on the purpose of use, but is preferably 50% by weight or more, more preferably 70% by weight or more, particularly preferably. Is 90% by weight or more. When the ratio of the repeating unit containing the alicyclic structure in the alicyclic structure-containing polymer is within this range, it is preferable from the viewpoint of transparency and heat resistance of the film.
Specific examples of the cyclic olefin polymer include (1) norbornene-based polymer, (2) monocyclic cyclic olefin-based polymer, (3) cyclic conjugated diene-based polymer, and (4) vinyl alicyclic hydrocarbon-based polymer. Examples thereof include polymers and hydrides of (1) to (4). Among these, from the viewpoint of heat resistance, mechanical strength, and the like, hydrides of norbornene polymers, vinyl alicyclic hydrocarbon polymers, and hydrides thereof are preferable.
（１）ノルボルネン系重合体
ノルボルネン系重合体は、ノルボルネン系モノマーを開環重合によって得られるものと、付加重合によって得られるものに大別される。
ノルボルネン系モノマーとしては、ビシクロ［２．２．１］ヘプト−２−エン（慣用名：ノルボルネン）、トリシクロ［４．３．０１，６．１２，５］デカ−３，７−ジエン（慣用名ジシクロペンタジエン）、７，８−ベンゾトリシクロ［４．３．０．１２，５］デカ−３−エン（慣用名メタノテトラヒドロフルオレン：１，４−メタノ−１，４，４ａ，９ａ−テトラヒドロフルオレンともいう）、テトラシクロ［４．４．０．１２，５．１７，１０］ドデカ−３−エン（慣用名：テトラシクロドデセン）等の脂環化合物及びこれらに置換基（アルキル基、アルキレン基、アルキリデン基、アルコキシカルボニル基等）を有するものが挙げられる。
開環重合によって得られる重合体としては、ＺＥＯＮＥＸ（登録商標；日本ゼオン社製）、ＺＥＯＮＯＲ（登録商標；日本ゼオン社製）、ＡＲＴＯＮ（登録商標；ＪＳＲ社製）などの、ノルボルネン系モノマーの開環重合体水素添加物が挙げられ、付加重合体としては、ＡＰＥＬ（登録商標；三井化学社製）、ＴＯＰＡＳ（登録商標；ポリプラスチック社製）などのノルボルネン系モノマーとエチレンとの付加重合体が挙げられる。
これらの中でも、全光線透過率の高さなどから開環重合体水素添加物が好ましく、特に極性基を有しない開環重合体（ＺＥＯＮＥＸ、ＺＥＯＮＯＲ）が好ましい。
（２）単環の環状オレフィン系重合体
単環の環状オレフィン系重合体としては、例えば、シクロヘキセン、シクロヘプテン、シクロオクテンなどの単環の環状オレフィン系単量体の付加重合体を用いることができる。
（３）環状共役ジエン系重合体
環状共役ジエン系重合体としては、例えば、シクロペンタジエン、シクロヘキサジエンなどの環状共役ジエン系単量体を１，２−または１，４−付加重合した重合体及びその水素化物などを用いることができる。
(1) Norbornene-based polymers Norbornene-based polymers are roughly classified into those obtained by ring-opening polymerization of norbornene-based monomers and those obtained by addition polymerization.
Examples of the norbornene-based monomer include bicyclo [2.2.1] hept-2-ene (common name: norbornene), tricyclo [4.3.0 1,6 . 1 2,5 ] deca-3,7-diene (common name dicyclopentadiene), 7,8-benzotricyclo [4.3.0.1 2,5 ] dec-3-ene (common name methanotetrahydrofluorene) : 1,4-methano-1,4,4a, 9a-tetrahydrofluorene), tetracyclo [4.4.0.1 2,5 . And an alicyclic compound such as 17, 10 ] dodec-3-ene (common name: tetracyclododecene) and those having a substituent (alkyl group, alkylene group, alkylidene group, alkoxycarbonyl group, etc.). .
Examples of polymers obtained by ring-opening polymerization include the opening of norbornene monomers such as ZEONEX (registered trademark; manufactured by Nippon Zeon), ZEONOR (registered trademark; manufactured by Nippon Zeon), and ARTON (registered trademark; manufactured by JSR). Examples of the addition polymer include addition polymers of norbornene monomers such as APEL (registered trademark; manufactured by Mitsui Chemicals), TOPAS (registered trademark; manufactured by Polyplastics) and ethylene. Can be mentioned.
Among these, a ring-opening polymer hydrogenated product is preferable from the viewpoint of high total light transmittance, and a ring-opening polymer having no polar group (ZEONEX, ZEONOR) is particularly preferable.
(2) Monocyclic cyclic olefin polymer As the monocyclic olefin polymer, for example, an addition polymer of a monocyclic olefin monomer such as cyclohexene, cycloheptene, or cyclooctene can be used. .
(3) Cyclic conjugated diene polymer As the cyclic conjugated diene polymer, for example, a polymer obtained by subjecting a cyclic conjugated diene monomer such as cyclopentadiene or cyclohexadiene to 1,2- or 1,4-addition polymerization, and The hydride can be used.
（４）ビニル脂環式炭化水素重合体
ビニル脂環式炭化水素重合体としては、例えば、ビニルシクロヘキセン、ビニルシクロヘキサンなどのビニル脂環式炭化水素系単量体の重合体及びその水素化物；スチレン、α−メチルスチレンなどのビニル芳香族系単量体の重合体の芳香環部分の水素化物；などが挙げられ、ビニル脂環式炭化水素重合体やビニル芳香族系単量体と、これらの単量体と共重合可能な他の単量体とのランダム共重合体、ブロック共重合体などの共重合体及びその水素化物など、いずれでもよい。ブロック共重合体としては、ジブロック、トリブロック、またはそれ以上のマルチブロックや傾斜ブロック共重合体などが挙げられ、特に制限はない。
(4) Vinyl alicyclic hydrocarbon polymer Examples of the vinyl alicyclic hydrocarbon polymer include polymers of vinyl alicyclic hydrocarbon monomers such as vinyl cyclohexene and vinyl cyclohexane and their hydrides; , Hydrides of aromatic ring moieties of polymers of vinyl aromatic monomers such as α-methylstyrene; and the like, and vinyl alicyclic hydrocarbon polymers and vinyl aromatic monomers, and these Any of random copolymers with other monomers copolymerizable with monomers, copolymers such as block copolymers, and hydrides thereof may be used. Examples of the block copolymer include diblock, triblock, or more multiblock and gradient block copolymers, and are not particularly limited.
本発明における基材フィルムとして用いることのできる樹脂のガラス転移温度（Ｔｇ）としては、１２０℃以上が好ましく、１４０℃以上であることがさらに好ましく、１６０℃以上であることが特に好ましい。ガラス転移温度がこのような範囲にある樹脂からなる基材は、高温下での使用における変形や応力が生じることがなく耐久性に優れる。基材の膜厚は、機械的強度などの観点から、好ましくは３０〜３００μｍ、より好ましくは５０〜２００μｍである。
基材フィルムのガラス転移温度は、ＪＩＳ Ｋ ７１２１に準じて測定する。
The glass transition temperature (Tg) of the resin that can be used as the base film in the present invention is preferably 120 ° C. or higher, more preferably 140 ° C. or higher, and particularly preferably 160 ° C. or higher. A substrate made of a resin having a glass transition temperature in such a range is excellent in durability without causing deformation or stress in use at high temperatures. The film thickness of the substrate is preferably 30 to 300 μm, more preferably 50 to 200 μm, from the viewpoint of mechanical strength and the like.
The glass transition temperature of the substrate film is measured according to JIS K7121.
本発明における基材フィルムとして用いることのできる樹脂の吸水率としては、０．０５％以下が好ましく、０．０３％以下であることがさらに好ましく、０．０１％以下であることが特に好ましい。吸水率が０．０１重量％を超えると、無機化合物からなる層やその他の層と樹脂フィルム基材との密着性が低くなり、長期間の使用において前記層の剥離が生じやすくなる。さらに、水分により真空排気に時間を要したり、無機化合物からなる層やその他の層が変質したりして、生産性や歩留まりが低下するおそれがある。
基材フィルムの吸水率は、ＪＩＳ Ｋ ７２０９に準じて測定する。
The water absorption of the resin that can be used as the base film in the present invention is preferably 0.05% or less, more preferably 0.03% or less, and particularly preferably 0.01% or less. When the water absorption exceeds 0.01% by weight, the adhesion between the layer made of an inorganic compound and other layers and the resin film substrate is lowered, and the layer is likely to be peeled off during long-term use. Furthermore, there is a possibility that productivity and yield may be lowered due to the time required for evacuation due to moisture, or a layer made of an inorganic compound or other layers may be altered.
The water absorption rate of the base film is measured according to JIS K 7209.
前記基材フィルムは、必要に応じて、酸化防止剤、熱安定剤、光安定剤、紫外線吸収剤、帯電防止剤、分散剤、塩素捕捉剤、難燃剤、結晶化核剤、ブロッキング防止剤、防曇剤、離型剤、顔料、有機又は無機の充填材、中和剤、滑剤、分解剤、金属不活性化剤、汚染防止材、抗菌剤やその他の樹脂、熱可塑性エラストマ−などの公知の添加剤を発明の効果が損なわれない範囲で含有することができる。これらの添加剤は、熱可塑性樹脂１００重量部に対して、それぞれ、通常０〜５重量部、好ましくは０〜３重量部の範囲で配合される。 The base film is, if necessary, an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet absorber, an antistatic agent, a dispersant, a chlorine scavenger, a flame retardant, a crystallization nucleating agent, an antiblocking agent, Known antifogging agents, mold release agents, pigments, organic or inorganic fillers, neutralizing agents, lubricants, decomposition agents, metal deactivators, antifouling agents, antibacterial agents and other resins, thermoplastic elastomers, etc. These additives can be contained as long as the effects of the invention are not impaired. These additives are each usually added in an amount of 0 to 5 parts by weight, preferably 0 to 3 parts by weight, per 100 parts by weight of the thermoplastic resin.
前記基材フィルムとして、片面又は両面に表面改質処理を施したものを使用してもよい。表面改質処理を行うことにより、有機膜や無機膜との密着性を向上させることができる。表面改質処理としては、エネルギー線照射処理や薬品処理などが挙げられる。
エネルギー線照射処理としては、コロナ放電処理、プラズマ処理、電子線照射処理、紫外線照射処理などが挙げられ、処理効率の点等から、コロナ放電処理及びプラズマ処理、特にコロナ放電処理が好ましい。
As the substrate film, one having one or both surfaces subjected to surface modification treatment may be used. By performing the surface modification treatment, the adhesion with an organic film or an inorganic film can be improved. Examples of the surface modification treatment include energy beam irradiation treatment and chemical treatment.
Examples of the energy beam irradiation treatment include corona discharge treatment, plasma treatment, electron beam irradiation treatment, ultraviolet ray irradiation treatment, and the like. From the viewpoint of treatment efficiency, corona discharge treatment and plasma treatment, particularly corona discharge treatment is preferable.
基材フィルムは、溶液流延法又は溶融押出成形法によってして得ることができる。中でも、透明樹脂フィルム基材中の揮発性成分の含有量や厚さムラを少なくできる点から、溶融押出成形法が好ましい。さらに溶融押出成形法としては、ダイスを用いる方法やインフレ−ション法などが挙げられるが、厚さ精度や生産性に優れる点でダイス、特にＴダイを用いる方法が好ましい。 The base film can be obtained by a solution casting method or a melt extrusion method. Among these, the melt extrusion molding method is preferable because the content of volatile components in the transparent resin film substrate and the thickness unevenness can be reduced. Further, examples of the melt extrusion molding method include a method using a die and an inflation method, but a method using a die, particularly a T die, is preferable in terms of excellent thickness accuracy and productivity.
（無機膜の構成）
本発明の透明ガスバリア性フィルムを構成する無機膜の構成について説明する。無機膜としては、透明性を有しかつ酸素、水蒸気等のガスバリア性を有する物であればよく、例えば、酸化アルミニウム、酸化硅素、酸化マグネシウム、酸化カルシウム、酸化ジルコニウム、酸化チタン、酸化ホウ素、酸化ハフニウム、酸化バリウム、酸化炭化珪素、二酸化珪素等の酸化物であり、特に、バリア性、生産性の点などから、酸化珪素、酸化窒化珪素、窒化珪素のいずれか好ましい。
(Structure of inorganic film)
The structure of the inorganic film which comprises the transparent gas barrier film of this invention is demonstrated. The inorganic film only needs to be transparent and have a gas barrier property such as oxygen and water vapor. For example, aluminum oxide, silicon oxide, magnesium oxide, calcium oxide, zirconium oxide, titanium oxide, boron oxide, oxidation Oxides such as hafnium, barium oxide, silicon oxide carbide, and silicon dioxide are preferable, and silicon oxide, silicon oxynitride, and silicon nitride are particularly preferable from the viewpoint of barrier properties and productivity.
無機膜の膜厚は、用いる無機化合物の種類や構成により適宜、選択すればよいが、一般的には５〜３００ｎｍが好ましく、望ましい。３００ｎｍを超えると、薄膜のフレキシビリティ性が低下し、成膜後に折り曲げ、引っ張りなどの外力で、薄膜に亀裂を生じる恐れがあり、透明性が低下したりし、また、材料自身の応力が大きくなり、フレキシビリティが損なわれたり、着色したりする、また、生産性を著しく低下させるので好ましくない。５ｎｍ以下では、透明性がよいが、均一な膜が得られにくく、膜厚が充分ではないことがあり、ガスバリア性の機能を十分に果たすことができない。上記の点から、１０〜１００ｎｍの膜厚がさらに好ましい。なお、金属蒸着膜の膜厚はリガク社製の蛍光Ｘ線分析装置：ＲＩＸ−３０００を用いて測定した。 The film thickness of the inorganic film may be appropriately selected depending on the type and configuration of the inorganic compound to be used, but generally 5 to 300 nm is preferable and desirable. If it exceeds 300 nm, the flexibility of the thin film will be reduced, and there is a risk that the thin film will be cracked by external forces such as bending and pulling after film formation, transparency will be reduced, and the stress of the material itself will be large. Therefore, flexibility is impaired or colored, and productivity is remarkably lowered. If it is 5 nm or less, the transparency is good, but it is difficult to obtain a uniform film, the film thickness may not be sufficient, and the gas barrier function cannot be sufficiently achieved. From the above points, a film thickness of 10 to 100 nm is more preferable. In addition, the film thickness of the metal vapor deposition film was measured using a fluorescent X-ray analyzer: RIX-3000 manufactured by Rigaku Corporation.
無機膜の形成は１又は複数回繰り返してもよく、両面に形成してもよい。両面に層を形成することにより、片側だけ膜を形成した際に発生する応力を相殺或いは緩和して、加熱を含む後加工工程、使用環境での歪み、反り（湾曲、カールともいう）などを防止することができるので、直角精度、寸法精度、部分場所における寸法精度が向上されることができる。さらに、フレキシブル性の偏りがなくなり、利用上の不具合がなくなる。 The formation of the inorganic film may be repeated one or more times, or may be formed on both sides. By forming layers on both sides, the stress generated when the film is formed on only one side is offset or relaxed, post-processing steps including heating, distortion in the environment of use, warping (also called bending or curling), etc. Therefore, the right-angle accuracy, the dimensional accuracy, and the dimensional accuracy at the partial location can be improved. Furthermore, there is no bias in flexibility and there are no problems in use.
（透明ガスバリアフィルムの形成方法）
本発明における透明ガスバリア性フィルムの形成方法について説明する。本発明におけるガスバリア層は、シートプラズマ装置を用いたスパッタイオンプレーティング法で、無機膜を成膜して得られる。シートプラズマ装置としては、特開２００７−１５４２６５号公報に詳述される、プラズマガンの放電電流とターゲット・バイアス電圧値を個別に制御し、プラズマガンで発生した円柱状のアルゴンプラズマを磁場でシート状に成形した高プラズマ密度のシートプラズマ装置が採用される。
シートプラズマ装置を用いたスパッタイオンプレーティング法は、プラズマの輸送方向の中心に対して略等密度分布するソースプラズマを放電により形成して、前記ソースプラズマを前記輸送方向に向けて放出可能なプラズマガンと、前記輸送方向に延びた輸送空間を有するシートプラズマ変形室と、互いに同極同士を向き合わせて、前記輸送空間を挟むように配置される第１の磁界発生手段の対と、前記輸送空間に連通した成膜空間を有する成膜室と、互いに異極同士を向き合わせて、前記成膜空間を挟むように配置される第２の磁界発生手段の対と、を備えて構成された装置を用いる。前記ソースプラズマは、前記輸送空間を移動する間に、前記第１の磁界発生手段の対の磁界により前記中心を含む主面に沿ってシート状に拡がり、前記シート状のプラズマは、前記成膜空間を移動する間に、前記第２の磁界発生手段の対の磁界により前記主面から凸状に偏倚する。シートプラズマをその主面から磁界に基づき凸状に偏倚させることにより、従来の成膜法によって成膜した場合と比較して、フィルム基材に対するプラズマダメージを大幅に減少させることができ、フィルムの透明性などを向上させることができる。
(Method for forming transparent gas barrier film)
The formation method of the transparent gas barrier film in this invention is demonstrated. The gas barrier layer in the present invention is obtained by forming an inorganic film by sputtering ion plating using a sheet plasma apparatus. As a sheet plasma apparatus, a discharge current and a target bias voltage value of a plasma gun, which are described in detail in Japanese Patent Application Laid-Open No. 2007-154265, are individually controlled, and a cylindrical argon plasma generated by the plasma gun is sheeted by a magnetic field. A high-plasma-density sheet plasma apparatus formed into a shape is employed.
Sputter ion plating using a sheet plasma apparatus is a plasma in which a source plasma having a substantially equal density distribution with respect to the center in the plasma transport direction is formed by discharge, and the source plasma can be emitted in the transport direction. A pair of guns, a sheet plasma deformation chamber having a transport space extending in the transport direction, a pair of first magnetic field generating means arranged so that the same poles face each other and sandwich the transport space, and the transport A film forming chamber having a film forming space communicating with the space, and a pair of second magnetic field generating means disposed so as to sandwich the film forming space with the opposite polarities facing each other. Use the device. The source plasma spreads in a sheet shape along the main surface including the center by the pair of magnetic fields of the first magnetic field generating means while moving in the transport space, and the sheet plasma is formed into the film. While moving in the space, the second magnetic field generating means is biased in a convex shape from the main surface by the pair of magnetic fields. By deviating the sheet plasma from its main surface in a convex shape based on a magnetic field, plasma damage to the film substrate can be greatly reduced as compared with the case of film formation by a conventional film formation method. Transparency etc. can be improved.
（透明ガスバリア性フィルム）
次に本発明における透明ガスバリア性フィルムについて説明する。
本発明における透明ガスバリア性フィルムは、上述したフィルム基材上に、無機層を形成したプラスチックフィルムである。本発明によれば、フィルム基材上に上記装置を用いたシートプラズマを用いたスパッタイオンプレーティング法で無機ターゲットを使用し、アルゴンガス雰囲気下でガスバリア層を形成すると、透明性が高く、寸法安定性に優れ、高い水蒸気バリア性を有するフィルムの形成が可能である。
(Transparent gas barrier film)
Next, the transparent gas barrier film in the present invention will be described.
The transparent gas barrier film in the present invention is a plastic film in which an inorganic layer is formed on the above-described film substrate. According to the present invention, when an inorganic target is used in a sputtering ion plating method using a sheet plasma using the above apparatus on a film substrate and a gas barrier layer is formed in an argon gas atmosphere, the transparency is high and the dimensions are high. A film having excellent stability and a high water vapor barrier property can be formed.
このような本発明の透明ガスバリア性フィルムの透明度としては、ＡＳＴＭ Ｄ１００３に基づく全光線透過率が、好ましくは７０％以上、より好ましくは８０％以上である。全光線透過率が低すぎると透明用途に使用しにくくなるおそれがある。 As the transparency of such a transparent gas barrier film of the present invention, the total light transmittance based on ASTM D1003 is preferably 70% or more, more preferably 80% or more. If the total light transmittance is too low, it may be difficult to use for transparent purposes.
このような本発明の透明ガスバリア性フィルムは、極めて優れた水蒸気バリア性を発揮する。水蒸気透過率としては、０．３ｇ／ｍ２／ｄａｙ以下、より好ましくは水蒸気透過率が０．１ｇ／ｍ２／ｄａｙ以下が好ましい。本発明のガスバリア性フィルムは、内容物の品質を変化させる原因となる水蒸気をほとんど透過させないので、高いガスバリア性が要求される用途、例えば食品や医薬品等の包装材料やパッケージ材料、有機エレクトロルミネッセンス表示素子や液晶表示素子などの光学素子等に好ましく用いることができる。 Such a transparent gas barrier film of the present invention exhibits extremely excellent water vapor barrier properties. The water vapor transmission rate is preferably 0.3 g / m 2 / day or less, and more preferably the water vapor transmission rate is 0.1 g / m 2 / day or less. The gas barrier film of the present invention hardly permeates water vapor that causes the quality of the contents to change, so that the application requires high gas barrier properties, such as packaging materials and packaging materials such as foods and pharmaceuticals, organic electroluminescence display It can be preferably used for an optical element such as an element or a liquid crystal display element.
（光学素子）
本発明の光学素子は、上記透明ガスバリア性フィルムを用いて作製することができる。すなわち、上記透明ガスバリア性フィルム基板の上に電圧または電流の変化によって光学的な特性が変化する素子を形成して、光学素子を作製することができる。また、上記透明ガスバリア性フィルム基板の上に、透明電極層、発光層、および陰極層を順次積層して、エレクトロルミネッセンス表示素子を作製することができる。
(Optical element)
The optical element of the present invention can be produced using the transparent gas barrier film. That is, an optical element can be produced by forming an element whose optical characteristics change with a change in voltage or current on the transparent gas barrier film substrate. Moreover, a transparent electrode layer, a light emitting layer, and a cathode layer can be laminated | stacked in order on the said transparent gas barrier film substrate, and an electroluminescent display element can be produced.
（エレクトロルミネッセンス素子）
次に、本発明のエレクトロルミネッセンス素子の構造と作製法について説明する。図２および図３は、それぞれ本発明のエレクトロルミネッセンス素子の一例の模式的断面図である。図２において、エレクトロルミネッセンス素子は、透明ガスバリア性フィルム基板２１上に、透明電極層２２、発光層２３、陰極層２４が順次積層され、その積層体が金属材料、プラスチック等で形成された封止材２５ａによって密閉された空間に封止された構造を有している。また、図３においては、図２に示したものと同一の構成を有する積層体が透明ガスバリア性フィルム等の樹脂材料よりなる封止材２５ｂによって封止されている。
本発明のエレクトロルミネッセンス表示素子において、透明ガスバリア性フィルム基板２１としては、上記した本発明の透明ガスバリア性フィルム基板が使用される。
(Electroluminescence element)
Next, the structure and manufacturing method of the electroluminescence element of the present invention will be described. 2 and 3 are schematic cross-sectional views of examples of the electroluminescence element of the present invention. In FIG. 2, the electroluminescent element is a sealing in which a
In the electroluminescence display element of the present invention, as the transparent gas
透明電極層は、発光層に正孔を供給する陽極としての機能を有するものであって、例えば、酸化錫、酸化亜鉛、酸化インジウム、酸化インジウム錫（ＩＴＯ）、酸化亜鉛インジウム（ＩＺＯ）等の導電性金属酸化物や金、銀、アルミニウム等の金属を用いることができ、その形状、構造、大きさ等についても特に制限されるものではない。透明電極層の作製法は、真空蒸着法、スパッタリング法、イオンプレーティング法、ＣＶＤ法、プラズマＣＶＤ法等の中から前記材料との適性を考慮して適宜選択すればよい。透明電極層のパターニングは、フォトリソグラフィーによる化学的エッチング法、レーザー等による物理的エッチング法、マスクを用いる真空蒸着法やスパッタリング法、又はリフトオフ法や印刷法等により行うことができる。厚さは、１０ｎｍ〜５μｍの範囲が適当である。 The transparent electrode layer has a function as an anode for supplying holes to the light emitting layer. For example, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), etc. Metals such as conductive metal oxides, gold, silver, and aluminum can be used, and the shape, structure, size, and the like are not particularly limited. The method for producing the transparent electrode layer may be appropriately selected from the vacuum deposition method, the sputtering method, the ion plating method, the CVD method, the plasma CVD method and the like in consideration of suitability with the material. The patterning of the transparent electrode layer can be performed by a chemical etching method using photolithography, a physical etching method using a laser, a vacuum evaporation method using a mask, a sputtering method, a lift-off method, a printing method, or the like. The thickness is suitably in the range of 10 nm to 5 μm.
発光層は、少なくとも１種の発光材を含有するものであり、必要に応じて、正孔や電子の発生や移動を容易にする正孔注入材、正孔輸送材、電子注入材、電子輸送材等を含有させてもよい。また、正孔注入材、正孔輸送材、電子注入材、電子輸送材等は、発光層とは別の層に含有させて、発光層に積層された状態であっても構わない。発光材としては、ベンゾオキサゾール誘導体、ベンゾイミダゾール誘導体、ベンゾチアゾール誘導体、スチリルベンゼン誘導体、ポリフェニル誘導体、ジフェニルブタジエン誘導体、テトラフェニルブタジエン誘導体、ナフタルイミド誘導体、クマリン誘導体、ペリレン誘導体、ペリノン誘導体、オキサジアゾール誘導体、アルダジン誘導体、ピラリジン誘導体、シクロペンタジエン誘導体、ビススチリルアントラセン誘導体、キナクリドン誘導体、ピロロピリジン誘導体、チアジアゾロピリジン誘導体、スチリルアミン誘導体、芳香族ジメチリデン誘導体、８−キノリール誘導体の金属錯体や希土類錯体に代表される各種金属錯体、ポリチオフェン誘導体、ポリフェニレン誘導体、ポリフェニレンビニレン誘導体、ポリフルオレン誘導体などの高分子化合物があげられる。これらは一種又は二種以上を混合して用いることができる。 The light-emitting layer contains at least one light-emitting material, and if necessary, a hole injection material, a hole transport material, an electron injection material, and an electron transport that facilitate the generation and movement of holes and electrons. Materials and the like may be included. Further, the hole injecting material, the hole transporting material, the electron injecting material, the electron transporting material, and the like may be contained in a layer different from the light emitting layer and stacked on the light emitting layer. Examples of luminescent materials include benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives, perylene derivatives, perinone derivatives, oxadiazoles. Derivatives, aldazine derivatives, pyralidine derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, quinacridone derivatives, pyrrolopyridine derivatives, thiadiazolopyridine derivatives, styrylamine derivatives, aromatic dimethylidene derivatives, 8-quinolyl derivatives metal complexes and rare earth complexes Various representative metal complexes, polythiophene derivatives, polyphenylene derivatives, polyphenylene vinylene derivatives, polyfluorene derivatives, etc. Of the polymer compound and the like. These can be used alone or in combination of two or more.
正孔注入材および正孔輸送材としては、低分子正孔輸送材および高分子正孔輸送材のいずれも使用可能であり、陽極から正孔を注入する機能、正孔を輸送する機能、及び陰極から注入された電子を障壁する機能のいずれかを有していれば特に限定されるものではない。正孔輸送材としては、例えば、カルバゾール誘導体、トリアゾール誘導体、オキサゾール誘導体、オキサジアゾール誘導体、イミダゾール誘導体、ポリアリールアルカン誘導体、ピラゾリン誘導体、ピラゾロン誘導体、フェニレンジアミン誘導体、アリールアミン誘導体、アミノ置換カルコン誘導体、スチリルアントラセン誘導体、フルオレノン誘導体、ヒドラゾン誘導体、スチルベン誘導体、シラザン誘導体、芳香族第三アミン化合物、スチリルアミン化合物、芳香族ジメチリデン系化合物、ポルフィリン系化合物、ポリシラン系化合物、ポリ（Ｎ−ビニルカルバゾール）誘導体、アニリン系共重合体、チオフェンオリゴマー、ポリチオフェン等の導電性高分子オリゴマー、ポリチオフェン誘導体、ポリフェニレン誘導体、ポリフェニレンビニレン誘導体、ポリフルオレン誘導体等の高分子化合物等があげられる。これらは一種または二種以上を併用してもよい。 As the hole injecting material and the hole transporting material, both a low molecular hole transporting material and a polymer hole transporting material can be used, a function of injecting holes from the anode, a function of transporting holes, and There is no particular limitation as long as it has any function of blocking electrons injected from the cathode. Examples of hole transport materials include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, Styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidene compounds, porphyrin compounds, polysilane compounds, poly (N-vinylcarbazole) derivatives, Conductive polymer oligomer such as aniline copolymer, thiophene oligomer, polythiophene, polythiophene derivative, polyphenylene derivative, polyphenylene Vinylene derivatives, polymer compounds such as polyfluorene derivatives, and the like. These may be used alone or in combination of two or more.
電子注入材および電子輸送材としては、電子を輸送する機能、陽極から注入された正孔を障壁する機能のいずれかを有しているものであれば制限されることはなく、例えば、トリアゾール誘導体、オキサゾール誘導体、オキサジアゾール誘導体、フルオレノン誘導体、アントラキノジメタン誘導体、アントロン誘導体、ジフェニルキノン誘導体、チオピランジオキシド誘導体、カルボジイミド誘導体、フルオレニリデンメタン誘導体、ジスチリルピラジン誘導体、ナフタレンペリレン等の複素環テトラカルボン酸無水物、フタロシアニン誘導体、８−キノリノール誘導体の金属錯体、メタルフタロシアニン、ベンゾオキサゾールおよびベンゾジアゾールを配位子とする金属錯体に代表される各種金属錯体、アニリン系共重合体、チオフェンオリゴマー、ポリチオフェン誘導体、ポリフェニレン誘導体、ポリフェニレンビニレン誘導体、ポリフルオレン誘導体等の高分子化合物があげられる。これらは一種または二種以上を併用してもよい。 The electron injecting material and the electron transporting material are not limited as long as they have either a function of transporting electrons or a function of blocking holes injected from the anode. For example, triazole derivatives , Oxazole derivatives, oxadiazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, naphthaleneperylene, etc. Various metal complexes represented by ring tetracarboxylic acid anhydrides, metal complexes of phthalocyanine derivatives, 8-quinolinol derivatives, metal phthalocyanine, benzoxazole and benzodiazole ligands, aniline copolymers, thiophene Goma, polythiophene derivatives, polyphenylene derivatives, polyphenylene vinylene derivatives, polymer compounds such as polyfluorene derivatives. These may be used alone or in combination of two or more.
発光層の製膜は、蒸着やスパッタリング等の乾式法、ディッピング、スピンコーティング、ディップコーティング、キャスティング、ダイコーティング、ロールコーティング、バーコーティング、グラビアコーティング等の湿式法等のいずれかによって好適に行うことができる。これらの製膜法は、発光層の材料に応じて適宜選択することができる。発光層の膜厚は、一般に１ｎｍ〜１０μｍ、好ましくは１０ｎｍ〜１μｍの範囲に設定される。正孔注入層、正孔輸送層、電子注入層、電子輸送層も発光層の場合と同様の方法で作製することができる。陰極層は、形状、構造、大きさ等に特に制限はなく、発光層に電子を注入する電極として機能すればよい。その形状、構造、大きさ等も特に制限はないが、厚さは、１０ｎｍ〜５μｍの範囲が適当である。陰極層用の材料としては、アルカリ金属（例えばＬｉ、Ｎａ、Ｋ、Ｃｓ等）、アルカリ土類金属（例えばＭｇ、Ｃａ等）、金、銀、鉛、アルミニウム、ナトリウム−カリウム合金、リチウム−アルミニウム合金、マグネシウム−銀合金、インジウム、イッテルビウム等の希土類金属等が挙げられる。これらのなかから、二種以上併用しても構わない。陰極層の形成には、真空蒸着、スパッタリング、イオンプレーティング、ＣＶＤ、プラズマＣＶＤ等の手段を用いることができ、陰極の材料との適性を考慮して適宜選択すればよい。陰極のパターニングは、フォトリソグラフィー、レーザー等による物理的エッチング、マスクを用いる真空蒸着法やスパッタリング法、又はリフトオフ法や印刷法等を採用することができる。封止材としては、金属材料、プラスチック等で形成された封止材、例えばアルミニウム管など、公知のものが使用されるが、本発明における上記ガスバリアフィルム基板を封止材として使用してもよい。 The light emitting layer is preferably formed by any one of dry methods such as vapor deposition and sputtering, and wet methods such as dipping, spin coating, dip coating, casting, die coating, roll coating, bar coating, and gravure coating. it can. These film forming methods can be appropriately selected according to the material of the light emitting layer. The thickness of the light emitting layer is generally set in the range of 1 nm to 10 μm, preferably 10 nm to 1 μm. A hole injection layer, a hole transport layer, an electron injection layer, and an electron transport layer can also be produced in the same manner as in the case of the light emitting layer. The cathode layer is not particularly limited in shape, structure, size and the like, and may function as an electrode for injecting electrons into the light emitting layer. The shape, structure, size, etc. are not particularly limited, but the thickness is suitably in the range of 10 nm to 5 μm. Materials for the cathode layer include alkali metals (eg, Li, Na, K, Cs, etc.), alkaline earth metals (eg, Mg, Ca, etc.), gold, silver, lead, aluminum, sodium-potassium alloy, lithium-aluminum. Examples include alloys, magnesium-silver alloys, rare earth metals such as indium and ytterbium. Among these, two or more kinds may be used in combination. For the formation of the cathode layer, means such as vacuum vapor deposition, sputtering, ion plating, CVD, and plasma CVD can be used, and may be selected as appropriate in consideration of suitability with the material of the cathode. For the patterning of the cathode, physical etching using photolithography, laser, etc., vacuum deposition method using a mask, sputtering method, lift-off method, printing method, or the like can be employed. As the sealing material, a known material such as a sealing material formed of a metal material, plastic, or the like, for example, an aluminum tube is used. However, the gas barrier film substrate in the present invention may be used as the sealing material. .
上記で述べたエレクトロルミネッセンス表示素子以外にも、本発明の透明ガスバリア性フィルム基板は、それがもつ諸特性により、多くの製品に利用することができる。例えば、液晶表示素子、電子ペーパー用基板、電子デバイス用封止フィルム、レンズフィルム、導光板用フィルム、プリズムフィルム、位相差板・偏光板用フィルム、視野角補正フィルム、ＰＤＰ用フィルム、ＬＥＤ用フィルム、光通信用部材、タッチパネル用フィルム、各種機能性フィルムの基板、内部が透けて見える構造の電子機器用フィルム、ビデオディスク・ＣＤ／ＣＤ−Ｒ／ＣＤ−ＲＷ／ＤＶＤ／ＭＯ／ＭＤ・相変化ディスク・光カードを含む光記録メディア用フィルム、燃料電池用封止フィルム、太陽電池用フィルム等に使用することができる。 In addition to the electroluminescence display element described above, the transparent gas barrier film substrate of the present invention can be used for many products due to its various characteristics. For example, liquid crystal display elements, substrates for electronic paper, sealing films for electronic devices, lens films, films for light guide plates, prism films, retardation plate / polarizing plate films, viewing angle correction films, PDP films, LED films , Optical communication members, touch panel films, various functional film substrates, electronic device films with a transparent structure inside, video discs, CD / CD-R / CD-RW / DVD / MO / MD, phase change It can be used for films for optical recording media including disks and optical cards, sealing films for fuel cells, films for solar cells, and the like.
得られた透明ガスバリア性フィルムについて、水蒸気透過度測定を行って水蒸気バリア性を評価した。水蒸気透過度は、ＪＩＳ Ｋ ７１２９（Ａ法）に基づいて温度：４０℃、湿度：９０％ＲＨの条件下の水蒸気透過度を水蒸気透過度テスター（Ｌ８０−５０００型、ＬＹＳＳＹ社製）で測定した。
なお、本発明は、上記の実施の形態に限定されるものではない。上記実施形態は、例示であり、本発明の特許請求の範囲に記載された技術的思想と実質的に同一な構成を有し、同様な作用効果を奏するものは、いかなるものであっても本発明の技術的範囲に包含される。
About the obtained transparent gas barrier property film, water vapor permeability measurement was performed and water vapor barrier property was evaluated. The water vapor permeability was measured with a water vapor permeability tester (L80-5000, manufactured by LYSSY) under the conditions of temperature: 40 ° C. and humidity: 90% RH based on JIS K 7129 (Method A). .
The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.
以下、本発明を実施するための最良の形態を実施例に基づいて説明するが、本願発明はこれら実施例に限定されるものではない。
本実施例における評価は、以下の方法によって行う。
（１）ガラス転移温度
成膜前のフィルムを用い、ＪＩＳ Ｋ ７１２１に従い、ＤＳＣ法により測定した。
（２）飽和吸水率
ＪＩＳ Ｋ ７２０９に従い測定した。成膜前のフィルムを５０℃で２４時間乾燥し、デシケータ中で放冷し、次いでフィルムの乾燥質量（Ｍ１）を測定した。温度２３℃、相対湿度５０％の室内で、質量変化が無くなるまで（飽和するまで）フィルムを水に浸漬し、次いでフィルムの飽和吸水質量（Ｍ２）を測定した。これらの測定値から次式により飽和吸水率を求めた。
飽和吸水率（％）＝［（Ｍ２−Ｍ１）／Ｍ１］×１００
（３）水蒸気透過度
水蒸気透過度は、成膜後のフィルムを用い、ＪＩＳ Ｋ７１２９（Ａ法）に基づいて温度：４０℃、湿度：９０％ＲＨの条件下の水蒸気透過度を水蒸気透過度テスター（Ｌ８０−５０００型、ＬＹＳＳＹ社製）で測定した。
水蒸気透過度（ｇ・ｍ−２・ｄａｙ−１）が小さいと水蒸気バリア性が良好であることを示す。
（４）全光線透過率
ＡＳＴＭ Ｄ１００３に準拠して、成膜後のフィルムを用い、日本電色工業社製、「濁度計ＮＤＨ−２０００」にて測定した。
なお、任意の５箇所について測定を行い、その算術平均値を全光線透過率の代表値とした。
（５）膜厚
金属蒸着膜の膜厚は成膜後のフィルムを用い、リガク社製の蛍光Ｘ線分析装置：ＲＩＸ−３０００を用いて測定した。
Hereinafter, the best mode for carrying out the present invention will be described based on examples, but the present invention is not limited to these examples.
Evaluation in this example is performed by the following method.
(1) Glass transition temperature It measured by DSC method according to JISK7121 using the film before film-forming.
(2) Saturated water absorption Measured according to JIS K 7209. The film before film formation was dried at 50 ° C. for 24 hours, allowed to cool in a desiccator, and then the dry mass (M1) of the film was measured. The film was immersed in water in a room at a temperature of 23 ° C. and a relative humidity of 50% until there was no change in mass (until saturation), and then the saturated water absorption mass (M2) of the film was measured. From these measured values, the saturated water absorption was determined by the following equation.
Saturated water absorption (%) = [(M2-M1) / M1] × 100
(3) Water vapor transmission rate Water vapor transmission rate is a water vapor transmission rate tester using a film after film formation, and based on JIS K7129 (Method A), water vapor transmission rate under conditions of temperature: 40 ° C. and humidity: 90% RH. (L80-5000 type, manufactured by LYSSY).
If the water vapor permeability (g · m −2 · day −1 ) is small, it indicates that the water vapor barrier property is good.
(4) Total light transmittance Based on ASTM D1003, the film after film-forming was measured by Nippon Denshoku Industries Co., Ltd., "turbidimeter NDH-2000".
In addition, it measured about arbitrary 5 places and made the arithmetic mean value the representative value of the total light transmittance.
(5) Film thickness The film thickness of the metal vapor-deposited film was measured using a film after film formation, using a Rigaku fluorescent X-ray analyzer: RIX-3000.
実施例１
透明樹脂フィルム基材として、ゼオノア１６００（メタノテトラヒドロフルオレンとジシクロペンタジエンとの開環重合体水素添加物；Ｔｇ１６０℃）で作成された厚さ１００μｍの環状オレフィンポリマーフィルム（日本ゼオン社製）を用い、図１のシートプラズマ成膜装置（新明和工業社製）を用いたスパッタイオンプレーティング法により成膜を行った。装置の真空槽内に前記フィルムをセットし１０−４Ｐａ台まで真空引きした。前記シクロオレフィンポリマーフィルムのガラス転移温度は１６３℃、飽和吸水率は０．０１重量％以下であった。
（１）表側第一層の形成
放電ガスとしてアルゴンを分圧で０．０４Ｐａ導入、反応ガスとして酸素を分圧で０．０４Ｐａ導入した。雰囲気圧力が安定したところで放電を開始しシリコンターゲット上にシートプラズマを発生させ、スパッタリングプロセスを開始した。プロセスが安定したところでシャッターを開きフィルムへの酸化珪素の形成を開始した。５００Åの膜が堆積したところでシャッターを閉じて表側第一層を形成した。
（２）表側第二層の形成
反応ガスとして窒素を分圧で０．０４Ｐａ、酸素を分圧で０．０４Ｐａ導入した以外は上記（１）と同様にして表側第二層を形成した。
（３）裏側第一層の形成
前記フィルムを反転させて、反応ガスとして窒素を分圧で０．０４Ｐａ、酸素を窒素を分圧で０．０４Ｐａ導入した以外は上記（１）と同様にして裏側第一層を形成した。
その後、真空槽内に大気を導入し、表側第一層に酸化珪素、表側第二層に酸化窒化珪素、裏側に酸化窒化珪素からなる層を形成し蒸着フィルムを得た。表側の膜厚は１０００Å、裏側の膜厚は５００Åであった。
Example 1
As a transparent resin film substrate, a 100 μm thick cyclic olefin polymer film (manufactured by Nippon Zeon Co., Ltd.) made of ZEONOR 1600 (a ring-opening polymer hydrogenated product of methanotetrahydrofluorene and dicyclopentadiene; Tg 160 ° C.) is used. The film was formed by the sputter ion plating method using the sheet plasma film forming apparatus (manufactured by Shin Meiwa Kogyo Co., Ltd.) in FIG. The film was set in a vacuum chamber of the apparatus and evacuated to a level of 10 −4 Pa. The cycloolefin polymer film had a glass transition temperature of 163 ° C. and a saturated water absorption of 0.01% by weight or less.
(1) Formation of front side first layer Argon was introduced as a discharge gas at a partial pressure of 0.04 Pa, and oxygen was introduced as a reaction gas at a partial pressure of 0.04 Pa. When the atmospheric pressure was stabilized, discharge was started to generate sheet plasma on the silicon target, and the sputtering process was started. When the process was stable, the shutter was opened and formation of silicon oxide on the film was started. When the 500-mm film was deposited, the shutter was closed to form the front first layer.
(2) Formation of front side second layer A front side second layer was formed in the same manner as in the above (1) except that nitrogen was introduced as a reaction gas at a partial pressure of 0.04 Pa and oxygen was introduced at a partial pressure of 0.04 Pa.
(3) Formation of backside first layer The above film was inverted, and the same procedure as in (1) above was conducted, except that nitrogen was introduced as a reactive gas at a partial pressure of 0.04 Pa and oxygen was introduced at a partial pressure of 0.04 Pa. A backside first layer was formed.
Thereafter, air was introduced into the vacuum chamber, and a layer made of silicon oxide on the front side first layer, silicon oxynitride on the front side second layer, and silicon oxynitride on the back side was formed to obtain a vapor deposition film. The film thickness on the front side was 1000 mm, and the film thickness on the back side was 500 mm.
実施例２
表側第二層に窒化珪素、表側第三層に酸化窒化珪素からなる層を形成した以外は実施例1と同様にして蒸着フィルムを得た。表側の膜厚は１５００Å、裏側の膜厚は５００Åであった。
Example 2
A vapor-deposited film was obtained in the same manner as in Example 1, except that a silicon nitride layer was formed on the front second layer and a silicon oxynitride layer was formed on the front third layer. The film thickness on the front side was 1500 mm, and the film thickness on the back side was 500 mm.
実施例３
裏側に成膜を行わなかったこと以外は実施例2と同様にして蒸着フィルムを得た。表側の膜厚は１０００Åであった。
Example 3
A vapor-deposited film was obtained in the same manner as in Example 2 except that no film was formed on the back side. The film thickness on the front side was 1000 mm.
実施例４
（１）表側第一層の形成
放電ガスとしてアルゴンを分圧で０．０４Ｐａ導入、反応ガスとして酸素を分圧で０．０４Ｐａ導入した。雰囲気圧力が安定したところで放電を開始しアルミニウムターゲット上にシートプラズマを発生させ、スパッタリングプロセスを開始した。プロセスが安定したところでシャッターを開きフィルムへの酸化アルミニウムの形成を開始した。５００Åの膜が堆積したところでシャッターを閉じて表側第一層を形成した。
（２）表側第二層の形成
ターゲットとしてチタンを使用した以外は上記（１）と同様にして表側第二層を形成した。
（３）裏側第一層の形成
前期フィルムを反転させて、ターゲットとしてアルミニウムを使用した以外は上記（１）と同様にして裏側第一層を形成した。
その後、真空槽内に大気を導入し、表側第一層に酸化アルミニウム、表側第二層に酸化チタン、裏側に酸化アルミニウムからなる層を形成した以外は実施例1と同様にして蒸着フィルムを得た。表側の膜厚は１０００Å、裏側の膜厚は５００Åであった。
Example 4
(1) Formation of front side first layer Argon was introduced as a discharge gas at a partial pressure of 0.04 Pa, and oxygen was introduced as a reaction gas at a partial pressure of 0.04 Pa. When the atmospheric pressure was stabilized, discharge was started to generate sheet plasma on the aluminum target, and the sputtering process was started. When the process was stable, the shutter was opened and the formation of aluminum oxide on the film was started. When the 500-mm film was deposited, the shutter was closed to form the front first layer.
(2) Formation of front side second layer A front side second layer was formed in the same manner as in the above (1) except that titanium was used as a target.
(3) Formation of back side first layer The back side first layer was formed in the same manner as in the above (1) except that the film was inverted and aluminum was used as the target.
Thereafter, the atmosphere was introduced into the vacuum chamber, and a vapor deposition film was obtained in the same manner as in Example 1 except that a layer composed of aluminum oxide on the front side first layer, titanium oxide on the front side second layer, and aluminum oxide on the back side was formed. It was. The film thickness on the front side was 1000 mm, and the film thickness on the back side was 500 mm.
実施例５
透明樹脂フィルム基材として厚さ１００μｍのポリエーテルスルホンフィルムを用い、実施例２と同様にして蒸着フィルムを得た。表側の膜厚は１５００Å、裏側の膜厚は５００Åであった。前記ポリエーテルスルホンフィルムのガラス転移温度は２２０℃、飽和吸水率は０．４重量％であった。
Example 5
A vapor-deposited film was obtained in the same manner as in Example 2 using a polyethersulfone film having a thickness of 100 μm as the transparent resin film substrate. The film thickness on the front side was 1500 mm, and the film thickness on the back side was 500 mm. The polyether sulfone film had a glass transition temperature of 220 ° C. and a saturated water absorption of 0.4% by weight.
実施例６
透明樹脂フィルム基材として厚さ１００μｍのポリエチレンナフタレートフィルムを用い、実施例２と同様にして蒸着フィルムを得た。表側の膜厚は１５００Å、裏側の膜厚は５００Åであった。前記ポリエチレンナフタレートフィルムのガラス転移温度は１１８℃、飽和吸水率は０．２重量％であった。
Example 6
A vapor-deposited film was obtained in the same manner as in Example 2 using a 100 μm thick polyethylene naphthalate film as the transparent resin film substrate. The film thickness on the front side was 1500 mm, and the film thickness on the back side was 500 mm. The polyethylene naphthalate film had a glass transition temperature of 118 ° C. and a saturated water absorption of 0.2% by weight.
比較例１
厚さ１００μｍのシクロオレフィンポリマーフィルム（日本ゼオン社製：ゼオノア１６００で作成したフィルム）をそのまま用いて、水蒸気透過度および全光線透過率を測定した。
Comparative Example 1
Using a cycloolefin polymer film having a thickness of 100 μm (manufactured by ZEON Corporation: film made with ZEONOR 1600) as it was, the water vapor transmission rate and the total light transmittance were measured.
比較例２
透明樹脂フィルム基材として、ゼオノア１６００（メタノテトラヒドロフルオレンとジシクロペンタジエンとの開環重合体水素添加物）で作成された厚さ１００μｍの環状オレフィンポリマーフィルム（日本ゼオン社製）を用い、ロードロックを介して平行平板方式のプラズマＣＶＤ装置内のサンプルホルダーへと導入し、５×１０-7Ｔｏｒｒにまで排気を行った。続いて、サンプルホルダーを１５０℃にまで加熱し、１時間放置することにより脱ガスを行った。
（１）表側第一層の形成
に、サンプルホルダー温度を１５０℃に保ったまま、ＳｉＨ4 、Ｏ2 をそれぞれ１０、４００ｓｃｃｍ導入し、チャンバー内の圧力を２×１０−２ｔｏｒｒに保ち、１３．５６MHzの高周波電源を用い、投入電力を３００Ｗでフィルム上に酸化珪素膜を形成した。
（２）表側第二層の形成
次に、サンプルホルダー温度を１５０℃に保ったまま、ＳｉＨ４、ＮＨ３、Ｈ２、Ｏ２をそれぞれ１０、２０、４００ｓｃｃｍ導入し、チャンバー内の圧力を２×１０−２ｔｏｒｒに保ち、１３．５６ＭＨｚの高周波電源を用い、投入電力を３００Ｗでフィルム上に窒化珪素膜を形成した。
（３）表側第三層の形成
次に、サンプルホルダー温度を１５０℃に保ったまま、ＳｉＨ４、ＮＨ３、Ｈ２、Ｏ２をそれぞれ１０、２０、４００、４００ｓｃｃｍ導入し、チャンバー内の圧力を２×１０−２ｔｏｒｒに保ち、１３．５６ＭＨｚの高周波電源を用い、投入電力を３００Ｗでフィルム上に酸化窒化珪素膜を形成した。
（４）裏側第一層の形成
前期フィルムを反転させて、サンプルホルダー温度を１５０℃に保ったまま、ＳｉＨ４、ＮＨ３、Ｈ２、Ｏ２をそれぞれ１０、２０、４００、４００ｓｃｃｍ導入し、チャンバー内の圧力を２×１０−２ｔｏｒｒに保ち、１３．５６ＭＨｚの高周波電源を用い、投入電力を３００Ｗでフィルム上に酸化窒化珪素膜を形成した。
その後、真空槽内に大気を導入し、表側第一層に酸化珪素、表側第二層に窒化珪素、表側第三層に酸化窒化珪素、裏側に酸化窒化珪素からなる層を形成し蒸着フィルムを得た。表側の膜厚は１５００Å、裏側の膜厚は５００Åであった。
Comparative Example 2
As a transparent resin film base material, a 100 μm-thick cyclic olefin polymer film (manufactured by Nippon Zeon Co., Ltd.) made of ZEONOR 1600 (a ring-opening polymer hydrogenated product of methanotetrahydrofluorene and dicyclopentadiene) is used. Was introduced into a sample holder in a parallel plate type plasma CVD apparatus, and evacuated to 5 × 10 −7 Torr. Subsequently, the sample holder was heated to 150 ° C. and left for 1 hour for degassing.
(1) In the formation of the front side first layer, SiH 4 and O 2 were introduced at 10 and 400 sccm respectively while maintaining the sample holder temperature at 150 ° C., and the pressure in the chamber was maintained at 2 × 10 −2 torr. A silicon oxide film was formed on the film using a high frequency power source of .56 MHz and an input power of 300 W.
(2) Formation of front side second layer Next, SiH 4 , NH 3 , H 2 , and O 2 were introduced at 10, 20, and 400 sccm while maintaining the sample holder temperature at 150 ° C., and the pressure in the chamber was set to 2 A silicon nitride film was formed on the film at a power of 300 W using a high frequency power supply of 13.56 MHz while maintaining x10 −2 torr.
(3) Formation of front side third layer Next, SiH 4 , NH 3 , H 2 , and O 2 were introduced at 10, 20, 400 , and 400 sccm, respectively, while maintaining the sample holder temperature at 150 ° C., and the pressure in the chamber Was maintained at 2 × 10 −2 torr, and a silicon oxynitride film was formed on the film at a power of 300 W using a 13.56 MHz high frequency power source.
(4) Formation of back side first layer Inverting the previous film and introducing SiH 4 , NH 3 , H 2 , and O 2 at 10, 20, 400 , and 400 sccm respectively while maintaining the sample holder temperature at 150 ° C., The pressure in the chamber was kept at 2 × 10 −2 torr, and a silicon oxynitride film was formed on the film at a power of 300 W using a 13.56 MHz high frequency power source.
Then, air is introduced into the vacuum chamber, and a vapor deposition film is formed by forming a layer made of silicon oxide on the front side first layer, silicon nitride on the front side second layer, silicon oxynitride on the front side third layer, and silicon oxynitride on the back side. Obtained. The film thickness on the front side was 1500 mm, and the film thickness on the back side was 500 mm.
比較例３
透明樹脂フィルム基材として厚さ１００μｍのポリエーテルスルホンフィルムを用いた以外は、比較例２と同様にして蒸着フィルムを得た。表側の膜厚は１５００Å、裏側の膜厚は５００Åであった。
Comparative Example 3
A vapor deposition film was obtained in the same manner as in Comparative Example 2 except that a polyethersulfone film having a thickness of 100 μm was used as the transparent resin film substrate. The film thickness on the front side was 1500 mm, and the film thickness on the back side was 500 mm.
比較例４
透明樹脂フィルム基材として厚さ１００μｍのポリエチレンナフタレートフィルムを用いた以外は、比較例２と同様にして蒸着フィルムを得た。表側の膜厚は１５００Å、裏側の膜厚は５００Åであった。
Comparative Example 4
A vapor-deposited film was obtained in the same manner as in Comparative Example 2 except that a polyethylene naphthalate film having a thickness of 100 μm was used as the transparent resin film substrate. The film thickness on the front side was 1500 mm, and the film thickness on the back side was 500 mm.
実施例１〜６、比較例１〜４について、測定したデータを表１に示す。 Table 1 shows measured data for Examples 1 to 6 and Comparative Examples 1 to 4.
実施例１〜４では、環状オレフィンポリマー製フィルムに特定の装置を用いたスパッタイオンプレーティング法によって無機膜を形成することにより、いずれも良好な水蒸気透過度と、高い全光線透過率を示した。一方、比較例1では無機層が無いため、良好な水蒸気透過度が得られなかった。また、比較例２では、本発明の要件を満たさないプラズマＣＶＤ法を用いたので、高い全光線透過率を得ることが出来なかった。ポリエーテルサルホン製フィルムやポリエチレンナフタレート製フィルムは、環状オレフィンポリマー製フィルムに比べて水蒸気透過性が高いが、特定の装置を用いたスパッタイオンプレーティング法を採用すると、プラズマＣＶＤ法を採用した場合に比べて、水蒸気透過度を低くすることができる（実施例４、５、比較例３、４）。 In Examples 1 to 4, by forming an inorganic film by a sputter ion plating method using a specific apparatus on a film made of a cyclic olefin polymer, both showed good water vapor permeability and high total light transmittance. . On the other hand, in Comparative Example 1, since there was no inorganic layer, good water vapor permeability could not be obtained. Moreover, in the comparative example 2, since the plasma CVD method which does not satisfy the requirements of the present invention was used, a high total light transmittance could not be obtained. Polyethersulfone films and polyethylene naphthalate films have higher water vapor permeability than cyclic olefin polymer films, but when a sputter ion plating method using a specific device is employed, a plasma CVD method is employed. Compared with the case, water vapor permeability can be lowered (Examples 4 and 5, Comparative Examples 3 and 4).
１１ フランジ
１２ 第１の電磁コイル
２０ シートプラズマ変形室
２１ 輸送空間
２２ 円柱プラズマ
２３ 第２の電磁コイル
２４Ａ、２４Ｂ 棒磁石
２５、３６ 真空ポンプ
２６、３７ バルブ
２７ シートプラズマ
２７Ａ 湾曲部
２７Ｂ 頂点部
２８ ボトルネック部
２９ 通路
３０ 真空成膜室
３１ 成膜空間
３２ 第３の電磁コイル
３３ 第４の電磁コイル
３２Ａ、３３Ａ コイル面
３２Ｂ、３３Ｂ 法線
３４Ａ 基板ホルダ
３４Ｂ 基板
３５Ａ ターゲットホルダ
３５Ｂ ターゲット
３８ 永久磁石
４０ プラズマガン
５０ 配線溝
５１ Ｃｕ堆積膜
５２ 空孔
１００ シートプラズマ成膜装置
Ａ アノード
Ｋ カソード
Ｐ 輸送中心
Ｓ 主面
11
Claims (7)
プラズマの輸送方向の中心に対して略等密度分布するソースプラズマを放電により形成して、前記ソースプラズマを前記輸送方向に向けて放出可能なプラズマガンと、
前記輸送方向に延びた輸送空間を有するシートプラズマ変形室と、
互いに同極同士を向き合わせて、前記輸送空間を挟むように配置される第１の磁界発生手段の対と、
前記輸送空間に連通した成膜空間を有する成膜室と、
互いに異極同士を向き合わせて、前記成膜空間を挟むように配置される第２の磁界発生手段の対と、を備え、
前記ソースプラズマは、前記輸送空間を移動する間に、前記第１の磁界発生手段の対の磁界により前記中心を含む主面に沿ってシート状に拡がり、
前記シート状のプラズマは、前記成膜空間を移動する間に、前記第２の磁界発生手段の対の磁界により前記主面から凸状に偏倚する装置を用いたスパッタイオンプレーティング法によって形成されたことを特徴とする透明ガスバリア性フィルム。 A transparent gas barrier film having at least one inorganic film on at least one surface of a transparent plastic film, the inorganic film comprising:
A plasma gun capable of forming a source plasma having a substantially equal density distribution with respect to the center in the transport direction of the plasma by discharge, and discharging the source plasma in the transport direction;
A sheet plasma deformation chamber having a transport space extending in the transport direction;
A pair of first magnetic field generating means arranged to face each other with the same polarity and sandwich the transport space;
A film formation chamber having a film formation space communicating with the transport space;
A pair of second magnetic field generating means arranged so as to face each other different polarities and sandwich the film formation space,
The source plasma spreads in a sheet shape along the main surface including the center by the magnetic field of the pair of the first magnetic field generating means while moving in the transport space,
The sheet-like plasma is formed by a sputter ion plating method using an apparatus that is biased from the main surface by the magnetic field of the pair of the second magnetic field generating means while moving in the film formation space. A transparent gas barrier film characterized by the above.
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| JP2008020578A JP2009178956A (en) | 2008-01-31 | 2008-01-31 | Transparent gas barrier film and its use |
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| JP2008020578A JP2009178956A (en) | 2008-01-31 | 2008-01-31 | Transparent gas barrier film and its use |
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| JP2011042833A (en) * | 2009-08-21 | 2011-03-03 | Shinmaywa Industries Ltd | Sputtering apparatus and sputtering method |
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