JP2003053881A - Plastic film having water vapor barrier properties - Google Patents

Plastic film having water vapor barrier properties

Info

Publication number
JP2003053881A
JP2003053881A JP2001243096A JP2001243096A JP2003053881A JP 2003053881 A JP2003053881 A JP 2003053881A JP 2001243096 A JP2001243096 A JP 2001243096A JP 2001243096 A JP2001243096 A JP 2001243096A JP 2003053881 A JP2003053881 A JP 2003053881A
Authority
JP
Japan
Prior art keywords
water vapor
organic layer
vapor barrier
plastic film
film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP2001243096A
Other languages
Japanese (ja)
Inventor
Atsushi Sugizaki
敦 杉崎
Hisashi Ito
寿 伊東
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Bakelite Co Ltd
Original Assignee
Sumitomo Bakelite Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Bakelite Co Ltd filed Critical Sumitomo Bakelite Co Ltd
Priority to JP2001243096A priority Critical patent/JP2003053881A/en
Publication of JP2003053881A publication Critical patent/JP2003053881A/en
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/048—Forming gas barrier coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers

Abstract

PROBLEM TO BE SOLVED: To provide a transparent film which has a water vapor barrier performance higher than a usual one, and also does not deteriorate even when the film is bent. SOLUTION: The present plastic film having the water vapor barrier properties is obtained by a method wherein an organic layer and an inorganic layer, at least each one of them, are laminated alternately at least on one side of a base of a polymeric material by a vacuum film-making method and further the organic layer is crosslinked in a vacuum tank. The organic layer is constituted mainly of a polymer which is obtained by crosslinking monomers having an acryloyl group or a methacryloyl group and of which the factor of volume shrinkage due to a crosslinking reaction is smaller than 10%.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【発明の属する技術分野】本発明は、光学部材、エレク
トロニクス部材、一般包装部材、薬品包装部材などの幅
広い用途に応用が可能な透明で水蒸気バリア性の高いプ
ラスチック基板に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent plastic substrate having a high water vapor barrier property which can be applied to a wide range of applications such as optical members, electronic members, general packaging members, and chemical packaging members.

【０００２】[0002]

【従来の技術】従来より、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、水蒸気や酸素等の各種ガスの遮断を必要とする物
品の包装、食品や工業用品及び医薬品等の変質を防止す
るための包装用途に広く用いられている。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）基板等で使用されている。特に液晶表
示素子ＥＬ素子などへの応用が進んでいる透明基材に
は、近年、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よりも生産性が良
くコストダウンの点でも有利である。しかしながら、透
明プラスチック等のフィルム基材はガラスに対しガスバ
リア性が劣るという問題がある。ガスバリア性が劣る基
材を用いると、水蒸気や空気が浸透し、例えば液晶セル
内の液晶を劣化させ、表示欠陥となって表示品位を劣化
させてしまう。この様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。包装材や液晶表示素
子に使用されるガスバリア性フィルムとしてはプラスチ
ックフィルム上に酸化珪素を蒸着したもの（特公昭53-1
2953号公報）や酸化アルミニウムを蒸着したもの（特開
昭58-217344号公報）が知られており、いずれも１g/m2/
day程度の水蒸気バリア性を有する。近年では、液晶デ
ィスプレイの大型化、高精細ディスプレイ等の開発によ
りフィルム基板へのガスバリア性能について水蒸気バリ
アで0.1g/m2/day程度まで要求が上がってきている。こ
れに応えるためにより高いバリア性能が期待できる手段
としてスパッタリング法やＣＶＤ法による成膜検討が行
われている。2. Description of the Related Art Conventionally, a gas barrier film in which a thin film of a metal oxide such as aluminum oxide, magnesium oxide, or silicon oxide is formed on the surface of a plastic substrate or a film requires blocking of various gases such as water vapor and oxygen. It is widely used for packaging of products, and packaging for preventing deterioration of foods, industrial supplies, pharmaceuticals and the like. Further, it is used in liquid crystal display devices, solar cells, electroluminescence (EL) substrates, etc., in addition to packaging applications. Liquid crystal display elements In particular, transparent base materials, which have been increasingly applied to EL elements and the like, have recently been required to be lightweight and large in size, have long-term reliability and a high degree of freedom in shape, and can display curved surfaces. In addition to such high requirements, film base materials such as transparent plastics have begun to be used in place of glass substrates, which are heavy and easily cracked and difficult to increase in area. Further, the plastic film not only meets the above-mentioned requirements but also has the advantage of being more productive and cost-effective than glass since it can be used in a roll-to-roll system. However, there is a problem that a film base material such as a transparent plastic is inferior in gas barrier property to glass. If a base material having a poor gas barrier property is used, water vapor or air will permeate, for example, degrading the liquid crystal in the liquid crystal cell, resulting in a display defect and degrading the display quality. In order to solve such a problem, it is known to form a metal oxide thin film on a film substrate and use it as a gas barrier film substrate. A gas barrier film used for packaging materials and liquid crystal display devices is a plastic film on which silicon oxide is vapor-deposited (Japanese Patent Publication No. 53-1).
2953) and aluminum oxide vapor-deposited (Japanese Patent Application Laid-Open No. 58-217344), both of which are 1 g / m 2 /
It has a water vapor barrier property of about day. In recent years, the demand for gas barrier performance to film substrates has increased to about 0.1 g / m 2 / day for water vapor barrier due to the increase in size of liquid crystal displays and the development of high-definition displays. In order to respond to this, film forming studies by a sputtering method or a CVD method are being conducted as means for expecting higher barrier performance.

【０００３】ところが、ごく近年においてさらなるバリ
ア性を要求される有機ＥＬディスプレイや高精彩カラー
液晶ディスプレイなどの開発が進み、これに使用可能な
透明性を維持しつつもさらなる高バリア性特に水蒸気バ
リアで0.1g/m2/day未満の性能をもつ基材が要求される
ようになってきた。これらの要求に対し、有機層／無機
層の交互積層構造を有するバリア膜を真空蒸着法により
作製する技術がWO2000-26973に提案されている。ドライ
プロセスである真空蒸着は、溶媒を使用しないため高
純度の有機物薄膜が得られる、薄膜が容易に得られ膜
厚制御性が良いなどの特徴を有している。しかしなが
ら、フレキシブル表示デバイスに応用するための条件で
ある、曲げに対するバリア性能の劣化については十分な
検討がなされていない。In recent years, however, the development of organic EL displays and high-definition color liquid crystal displays, which are required to have further barrier properties, has progressed, and while maintaining the transparency that can be used for these, further high barrier properties, especially with a water vapor barrier. A base material having a performance of less than 0.1 g / m 2 / day has been required. To meet these requirements, WO2000-26973 proposes a technique for producing a barrier film having an alternating laminated structure of organic layers / inorganic layers by a vacuum vapor deposition method. Vacuum deposition, which is a dry process, has features such that a high-purity organic thin film can be obtained because a solvent is not used, and a thin film can be easily obtained and film thickness controllability is good. However, the deterioration of the barrier performance against bending, which is a condition for application to a flexible display device, has not been sufficiently studied.

【０００４】[0004]

【発明が解決しようとする課題】本発明の目的は、従来
よりも高い水蒸気バリア性能を持ちかつ曲げてもそのバ
リア性能が劣 化しない透明フィルムを提供することに
ある。SUMMARY OF THE INVENTION An object of the present invention is to provide a transparent film which has a higher water vapor barrier performance than ever and does not deteriorate even when bent.

【０００５】[0005]

【課題を解決するための手段】すなわち本発明は、 （１）高分子材料からなるフィルムの少なくとも片面
に、真空製膜法により有機層と無機層とが交互に少なく
とも一層以上積層され、更に真空槽内で前記有機層を架
橋させることにより得られる水蒸気バリア性プラスチッ
クフィルムであり、前記有機層がアクリロイル基または
メタクリロイル基を有するモノマーを架橋させて得られ
る架橋反応による体積収縮率が１０％より小さ高分子を
主成分とする水蒸気バリア性フィルム。 （２）有機層が２官能以上のアクリロイル基またはメタ
クリロイル基を有する１種類以上のモノマー、または２
官能以上のアクリロイル基またはメタクリロイル基を有
する１種類以上のモノマーと単官能以上のアクリロイル
基またはメタクリロイル基を有する1種類以上のモノマ
ーとの混合物を、架橋させて得られる高分子を主成分と
する（１）の水蒸気バリア性プラスチックフィルム。 （３）２官能以上のアクリロイル基またはメタクリロイ
ル基を有するモノマーが２官能以上のイソシアヌル酸ア
クリレートまたはエポキシアクリレートまたはウレタン
アクリレートである（２）の水蒸気バリア性プラスチッ
クフィルム。 （４）有機層の厚みが１０〜１０００ｎｍである（１）
〜（３）の水蒸気バリア性プラスチックフィルム。 （５）無機層が珪素酸化物または珪素窒化物または珪素
窒化酸化物を主成分とする（１）〜（４）の水蒸気バリ
ア性プラスチックフィルム。 （６）基材のガラス転移温度が200℃以上である（１）
〜（５）の水蒸気バリア性プラスチックフィルム。 （７）基材がノルボルネン系樹脂またはポリエーテルス
ルホンを主成分とする（１）〜（６）の水蒸気バリア性
プラスチックフィルム。 である。Means for Solving the Problems That is, the present invention is as follows. (1) At least one or more organic layers and inorganic layers are alternately laminated by a vacuum film forming method on at least one surface of a film made of a polymer material, and further vacuum A water vapor barrier plastic film obtained by cross-linking the organic layer in a tank, wherein the organic layer has a volume shrinkage rate of less than 10% by a cross-linking reaction obtained by cross-linking a monomer having an acryloyl group or a methacryloyl group. A water vapor barrier film whose main component is a polymer. (2) One or more kinds of monomers whose organic layer has a bifunctional or more functional acryloyl group or methacryloyl group, or 2
A polymer obtained by crosslinking a mixture of one or more kinds of monomers having a functional or higher acryloyl group or methacryloyl group and one or more kinds of monomers having a monofunctional or higher acryloyl group or methacryloyl group as a main component ( The water vapor barrier plastic film of 1). (3) The water vapor barrier plastic film according to (2), wherein the monomer having a bifunctional or higher functional acryloyl group or a methacryloyl group is a bifunctional or higher functional isocyanuric acid acrylate, epoxy acrylate or urethane acrylate. (4) The thickness of the organic layer is 10 to 1000 nm (1)
Water vapor barrier plastic film of (3). (5) The water vapor barrier plastic film according to (1) to (4), wherein the inorganic layer contains silicon oxide, silicon nitride or silicon nitride oxide as a main component. (6) The glass transition temperature of the substrate is 200 ° C or higher (1)
~ (5) Water vapor barrier plastic film. (7) The water vapor barrier plastic film according to any one of (1) to (6), wherein the base material is a norbornene-based resin or polyether sulfone as a main component. Is.

【０００６】[0006]

【発明の実施の形態】本発明は、樹脂基材上にアクリル
系モノマーを真空蒸着法により成膜した後に、直ちに架
橋反応させ高分子膜の有機層を形成させ、更に無機層を
真空製膜法により有機層の表面に形成させる工程を繰り
返すことで大気下にフィルム表面を曝すことなく有機と
無機の交互積層バリア膜が作製できるバリア膜作製にお
いて、用いる有機層がアクリロイル基またはメタクリロ
イル基を有するモノマーを架橋させて得られる架橋反応
による体積収縮率が１０％より小さい高分子を主成分と
することにより、ガスバリア膜付きのフィルムに反りが
無く、曲げてもそのバリア性能を劣化させず、且つ良好
な無機層の密着性が得られる水蒸気バリア性プラスチッ
クフィルムである。有機層の架橋反応による体積収縮率
が１０％を越える場合は、架橋反応時の体積変化による
収縮応力が大きく発生し、フィルムの反りや付着界面で
の応力集中による密着不良やバリア層のクラック等の構
造欠陥が発生する。また、無機層だけでは無くしきれな
い層構造の欠陥部分を有機層で埋め、水蒸気バリア性を
高めることが可能である。さらに、有機層については、
その厚みが、１０ｎｍ〜１０００ｎｍが好ましい。有機
層の厚みが１０ｎｍより小さい場合は、有機層の厚みの
均一性を得ることが困難となるため、無機層の構造欠陥
を効率よく有機層で埋めることができずに、バリア性の
向上は見られない。また、１０００ｎｍを越える厚みの
場合は、曲げ等の外力により有機層がクラックを発生し
易くなるためバリア性が低下してしまう不具合が発生す
る。本発明の有機層は、アクリロイル基、メタクリロイ
ル基を有するモノマーを架橋させて得られる。。中で
も、エポキシ（メタ）アクリレート、ウレタン（メタ）
アクリレート、イソシアヌル酸（メタ）アクリレート、
ペンタエリスリトール（メタ）アクリレート、トリメチ
ロールプロパン（メタ）アクリレート、エチレングリコ
ール（メタ）アクリレート、ポリエステル（メタ）アク
リレートなどのうち、２官能以上のアクリロイル基また
はメタクリロイル基を有するモノマーを真空蒸着後、架
橋させて得られる高分子を主成分とすることが好まし
い。これらの２官能以上のアクリロイル基またはメタク
リロイル基を有するモノマーは２種類以上を混合して用
いる方法、また１官能の（メタ）アクリレートを混合し
て用いる方法は硬化収縮を小さく抑える点でより好まし
い。また、特に架橋度が高く、ガラス転移温度が200℃
以上である、イソシアヌル酸アクリレート、エポキシア
クリレート、ウレタンアクリレートを主成分とすること
が好ましい。本発明の有機物質モノマー成膜するための
真空成膜法は特に制限はないが、電子線蒸着、イオンプ
レーティング、フ゜ラス゛マＣＶＤ、ＤＣスハ゜ッタ、ＲＦスハ゜ッタ等
の成膜方法が好ましく、有機物質モノマーの成膜速度を
制御しやすい抵抗加熱蒸着法はより好ましい。本発明の
有機物質モノマーの架橋方法に関しては何らその制限は
ないが、電子線や紫外線等が真空槽内に容易に取り付け
られる点、架橋反応による高分子量化が迅速である点に
おいて好ましい。BEST MODE FOR CARRYING OUT THE INVENTION According to the present invention, an acrylic monomer is formed on a resin substrate by a vacuum deposition method, and then a cross-linking reaction is immediately performed to form an organic layer of a polymer film. By repeating the step of forming on the surface of the organic layer by the method, an organic-inorganic alternate laminated barrier film can be prepared without exposing the film surface to the atmosphere. In the barrier film preparation, the organic layer used has an acryloyl group or a methacryloyl group. By using as a main component a polymer having a volumetric shrinkage of less than 10% due to a crosslinking reaction obtained by crosslinking a monomer, the film with a gas barrier film has no warp and does not deteriorate its barrier performance even when bent, and It is a water vapor barrier plastic film capable of obtaining good adhesion of an inorganic layer. If the volumetric shrinkage rate due to the crosslinking reaction of the organic layer exceeds 10%, a large shrinkage stress occurs due to the volume change during the crosslinking reaction, resulting in film warpage or adhesion failure due to stress concentration at the adhesion interface, cracks in the barrier layer, etc. Structural defects occur. Further, it is possible to enhance the water vapor barrier property by filling the defective portion of the layer structure, which cannot be completely eliminated by only the inorganic layer, with the organic layer. Furthermore, regarding the organic layer,
The thickness is preferably 10 nm to 1000 nm. When the thickness of the organic layer is less than 10 nm, it becomes difficult to obtain the uniformity of the thickness of the organic layer, so that the structural defects of the inorganic layer cannot be efficiently filled with the organic layer, and the barrier property is improved. can not see. Further, when the thickness exceeds 1000 nm, cracks are likely to occur in the organic layer due to an external force such as bending, so that the barrier property is deteriorated. The organic layer of the present invention is obtained by crosslinking a monomer having an acryloyl group or a methacryloyl group. . Among them, epoxy (meth) acrylate, urethane (meth)
Acrylate, isocyanuric acid (meth) acrylate,
Among pentaerythritol (meth) acrylate, trimethylolpropane (meth) acrylate, ethylene glycol (meth) acrylate, polyester (meth) acrylate, etc., a monomer having a bifunctional or higher functional acryloyl group or methacryloyl group is vacuum-deposited and then crosslinked. It is preferable that the obtained polymer is a main component. The method of mixing two or more kinds of these monomers having a bifunctional or more acryloyl group or methacryloyl group and the method of mixing a monofunctional (meth) acrylate are more preferable from the viewpoint of suppressing the shrinkage upon curing. Also, the degree of crosslinking is particularly high, and the glass transition temperature is 200 ° C.
It is preferable that the main components are isocyanuric acid acrylate, epoxy acrylate, and urethane acrylate. The vacuum film forming method for forming the organic substance monomer film of the present invention is not particularly limited, but a film forming method such as electron beam evaporation, ion plating, plasma CVD, DC sputtering, RF sputtering and the like is preferable. The resistance heating vapor deposition method, in which the film formation rate is easily controlled, is more preferable. There is no limitation on the method of crosslinking the organic substance monomer of the present invention, but it is preferable in that electron beams, ultraviolet rays and the like can be easily attached to the inside of the vacuum chamber, and that the crosslinking reaction can rapidly increase the molecular weight.

【０００７】本発明の無機層に関しては何ら制限はない
が、例えばSi、Al、In、Sn、Zn、Ti、Cu、Ce等の１種以
上を含む酸化物もしくは窒化物もしくは酸化窒化物など
を用いることができる。無機層は厚すぎると曲げ応力に
よるクラックの恐れがあり、薄すぎると膜が島状に分布
するため、いずれも水蒸気バリア性が悪くなる。上記の
ことより、それぞれの無機層の厚みは5nm〜500nmの範囲
が好ましいが、特に限定はしない。また、それぞれの無
機層は同じ組成でも別の組成でも良く制限はない。水蒸
気バリア性と高透明性を両立させるには無機層として珪
素酸化物や珪素酸化窒化物を使うのが好ましい。また、
無機膜の成膜方法としては抵抗加熱蒸着法、電子線蒸着
法、イオンプレーティング法、ＣＶＤ法、スパッタリン
グ法が適用でき、目的の無機酸化物、無機窒化物、無機
窒化酸化物が得られる方法であれば制限はない。本発明
の樹脂基材としては何ら制限はないが、ポリスルホン樹
脂、ポリエーテルスルホン樹脂、ポリカーボネート樹
脂、ポリアリレート樹脂、ポリアクリレート樹脂、ポリ
エステル樹脂、ポリアミド樹脂、エポキシ樹脂、ポリイ
ミド樹脂、ポリオレフィン樹脂、ポリ塩化ビニリデン樹
脂等を使用することができる。特に、ガラス転移温度が
２００℃以上のノルボルネン系樹脂やポリエーテルサル
ホンは光学特性が良好で耐熱性が高く、有機層−無機層
形成プロセスにおいて高温処理による変形や劣化が無い
ので好ましい。There is no limitation on the inorganic layer of the present invention. For example, an oxide, a nitride or an oxynitride containing one or more of Si, Al, In, Sn, Zn, Ti, Cu, Ce and the like is used. Can be used. If the inorganic layer is too thick, there is a risk of cracks due to bending stress, and if it is too thin, the film will be distributed in islands, and the water vapor barrier property will deteriorate in both cases. From the above, the thickness of each inorganic layer is preferably in the range of 5 nm to 500 nm, but is not particularly limited. Further, the respective inorganic layers may have the same composition or different compositions, and there is no limitation. In order to achieve both the water vapor barrier property and high transparency, it is preferable to use silicon oxide or silicon oxynitride as the inorganic layer. Also,
As a method for forming an inorganic film, a resistance heating evaporation method, an electron beam evaporation method, an ion plating method, a CVD method, a sputtering method can be applied, and a desired inorganic oxide, inorganic nitride, or inorganic nitride oxide can be obtained. If so, there is no limit. The resin base material of the present invention is not particularly limited, but polysulfone resin, polyether sulfone resin, polycarbonate resin, polyarylate resin, polyacrylate resin, polyester resin, polyamide resin, epoxy resin, polyimide resin, polyolefin resin, polychlorinated resin. Vinylidene resin or the like can be used. In particular, a norbornene-based resin having a glass transition temperature of 200 ° C. or higher and polyether sulfone are preferable because they have good optical characteristics and high heat resistance and are not deformed or deteriorated by high temperature treatment in the organic layer-inorganic layer forming process.

【０００８】[0008]

【実施例】以下本発明の実施例について詳細に説明する
が、本発明は、何ら下記実施例に限定されるものではな
い。 （実施例１）抵抗加熱端子及び電子銃を備えた真空蒸着
機内に高圧水銀ＵＶランプを取り付け成膜装置とした。
無機層として酸化珪素を用い、有機層として４官能のジ
ペンタエリスリトールペンタヘキサアクリレート(アロニック
スM-400：東亜合成社製)にラジカル開始剤（イルカ゛キュアー65
1：チハ゛カ゛イキ゛ー社製）を1wt%添加した未硬化樹脂を用い
た。この樹脂のガラス基板注形法により得たＵＶ架橋反
応による体積収縮率は3.5%であった。樹脂基板として0.
1mm厚のポリエーテルサルホンを真空槽内にセットし10
-4Pa台まで真空引きした後に、有機蒸着源の抵抗加熱を
開始し、不純物の蒸発が完了したところで蒸着シャッタ
ーを開き100nmの有機層を蒸着した。蒸着シャッターを
戻した後にＵＶランプのシャッターを開き、300mJ/cm2
の積算光量でモノマーを硬化した。真空槽内の真空度が
再び10-4Pa台で安定した後に、電子線蒸着法により50nm
の酸化珪素膜を形成した。以上の有機層蒸着／ＵＶ硬化
／無機層の電子線蒸着を、再度繰り返して樹脂基板／有
機層／無機層／有機層／無機層の水蒸気バリア性プラス
チックフィルムを成膜した。 （実施例２）実施例１で使用した４官能のアクリレート
の代わりに、 ＵＶ架橋反応による体積収縮率が3.8%で
ある３官能イソシアヌル酸EO変性トリアクリレート（アロ
ニックスM-315：東亜合成社製）を用いた他は実施例１と同
様に、ポリエーテルサルホンフィルム上に有機層/無機
層/有機層/無機層の形成を行った。 （実施例３）実施例１で使用した４官能のアクリレート
の代わりに、 ＵＶ架橋反応による体積収縮率が2.1%で
ある２官能のエポキシアクリレート（VR-60LAV：昭和高
分子社製）と４官能以上のウレタンアクリレート（ユニテ゛
ィック17-806：大日本インキ社製）の重量比３：２の樹脂混合
物を用いた他は実施例１と同様に、ポリエーテルサルホ
ンフィルム上に有機層/無機層/有機層/無機層の形成を
行った。 （実施例４）実施例１で使用した４官能のアクリレート
の代わりに、 ＵＶ架橋反応による体積収縮率が5.6%で
ある４官能のペンタエリスリトールテトラアクリレート
（アロニックスM-450：東亜合成社製）を用いた他は実施例１
と同様に、ポリエーテルサルホンフィルム上に有機層/
無機層/有機層/無機層の形成を行った。 （実施例５）実施例１で使用した４官能のアクリレート
の代わりに、 ＵＶ架橋反応による体積収縮率が3.6%で
ある４官能のジトリメチロールプロパンテトラアクリレ
ート（アロニックスM-408：東亜合成社製）を用いた他は実施
例１と同様に、ポリエーテルサルホンフィルム上に有機
層/無機層/有機層/無機層の形成を行った。 （実施例６）実施例１で使用した４官能のアクリレート
の代わりに、 ＵＶ架橋反応による体積収縮率が3.0%で
ある４官能のペンタエリスリトールテトラアクリレート
（アロニックスM-450：東亜合成社製）と単官能のフタル酸モ
ノヒドロキシエチルアクリレート（アロニックスM-5400：東亜
合成社製）の重量比９：１の樹脂混合物を用いた他は実
施例１と同様に、ポリエーテルサルホンフィルム上に有
機層/無機層/有機層/無機層の形成を行った。 （実施例７）実施例１で使用した４官能のアクリレート
の代わりに、 ＵＶ架橋反応による体積収縮率が2.9%で
ある３官能イソシアヌル酸EO変性トリアクリレート（アロ
ニックスM-315：東亜合成社製）と２官能のエポキシアクリ
レート（VR-60LAV：昭和高分子社製）の重量比４：１の
樹脂混合物を用いた他は実施例１と同様に、ポリエーテ
ルサルホンフィルム上に有機層/無機層/有機層/無機層
の形成を行った。EXAMPLES Examples of the present invention will be described in detail below, but the present invention is not limited to the following examples. (Example 1) A high pressure mercury UV lamp was installed in a vacuum vapor deposition machine equipped with a resistance heating terminal and an electron gun to form a film forming apparatus.
Silicon oxide is used as the inorganic layer, and a tetrafunctional dipentaerythritol pentahexaacrylate (Aronix M-400: manufactured by Toagosei Co., Ltd.) is used as an organic layer and a radical initiator (Irgacure 65
1: uncured resin added with 1 wt% of Ciba Geiger) was used. The volume shrinkage of this resin due to the UV crosslinking reaction obtained by the glass substrate casting method was 3.5%. As a resin substrate.
Set 1mm thick polyethersulfone in the vacuum chamber and
After evacuation to -4 Pa level, resistance heating of the organic vapor deposition source was started, and when the evaporation of impurities was completed, the vapor deposition shutter was opened to vapor deposit an organic layer of 100 nm. After returning the vapor deposition shutter, open the UV lamp shutter to 300 mJ / cm2.
The monomer was cured with the integrated light amount of. After the vacuum degree in the vacuum chamber was stabilized again at the level of 10 -4 Pa, 50 nm was obtained by electron beam evaporation.
A silicon oxide film was formed. The above vapor deposition of organic layer / UV curing / electron vapor deposition of inorganic layer was repeated again to form a water vapor barrier plastic film of resin substrate / organic layer / inorganic layer / organic layer / inorganic layer. (Example 2) Instead of the tetrafunctional acrylate used in Example 1, a trifunctional isocyanuric acid EO-modified triacrylate having a volume contraction rate of 3.8% by a UV crosslinking reaction (Aronix M-315: manufactured by Toagosei Co., Ltd.) In the same manner as in Example 1 except that was used, an organic layer / inorganic layer / organic layer / inorganic layer was formed on the polyether sulfone film. (Example 3) Instead of the tetrafunctional acrylate used in Example 1, a bifunctional epoxy acrylate (VR-60LAV: Showa High Polymer Co., Ltd.) having a volumetric shrinkage of 2.1% due to a UV crosslinking reaction and a tetrafunctional An organic layer / inorganic layer was formed on a polyethersulfone film in the same manner as in Example 1 except that the above-mentioned resin mixture of urethane acrylate (Unitic 17-806: manufactured by Dainippon Ink and Chemicals, Inc.) in a weight ratio of 3: 2 was used. / Organic layer / inorganic layer was formed. (Example 4) Instead of the tetrafunctional acrylate used in Example 1, a tetrafunctional pentaerythritol tetraacrylate (Aronix M-450: manufactured by Toagosei Co., Ltd.) having a volumetric shrinkage of 5.6% due to a UV crosslinking reaction was used. Example 1 other than the use
Similar to the organic layer / on the polyethersulfone film
Formation of inorganic layer / organic layer / inorganic layer was performed. (Example 5) Instead of the tetrafunctional acrylate used in Example 1, a tetrafunctional ditrimethylolpropane tetraacrylate having a volumetric shrinkage of 3.6% due to a UV crosslinking reaction (Aronix M-408: manufactured by Toagosei Co., Ltd.) In the same manner as in Example 1 except that was used, an organic layer / inorganic layer / organic layer / inorganic layer was formed on the polyether sulfone film. (Example 6) Instead of the tetrafunctional acrylate used in Example 1, a tetrafunctional pentaerythritol tetraacrylate (Aronix M-450: manufactured by Toagosei Co., Ltd.) having a volumetric shrinkage of 3.0% due to a UV crosslinking reaction was used. An organic layer was formed on the polyether sulfone film in the same manner as in Example 1 except that a resin mixture of monofunctional phthalic acid monohydroxyethyl acrylate (Aronix M-5400: manufactured by Toagosei Co., Ltd.) in a weight ratio of 9: 1 was used. / Inorganic layer / organic layer / inorganic layer was formed. (Example 7) Instead of the tetrafunctional acrylate used in Example 1, a trifunctional isocyanuric acid EO-modified triacrylate having a volume contraction rate of 2.9% by a UV crosslinking reaction (Aronix M-315: manufactured by Toagosei Co., Ltd.) Organic layer / inorganic layer on the polyethersulfone film in the same manner as in Example 1 except that a resin mixture having a weight ratio of 4: 1 of bifunctional epoxy acrylate (VR-60LAV: Showa High Polymer Co., Ltd.) was used. / Organic layer / inorganic layer was formed.

【０００９】（比較例１）実施例１で使用した４官能の
アクリレートの代わりに、 ＵＶ架橋反応による体積収
縮率が19.1%である２官能のネオペンチルグリコールジ
アクリレート（NKエステルA-NPG：新中村化学工業社製）を
用いた他は実施例１と同様に、ポリエーテルサルホンフ
ィルム上に有機層/無機層/有機層/無機層の形成を行っ
た。 （比較例２）実施例１で使用した４官能のアクリレート
の代わりに、 ＵＶ架橋反応による体積収縮率が15.5%で
ある２官能のトリプロピレングリコールジアクリレート
（NKエステルAPG-200：新中村化学工業社製）を用いた他は
実施例１と同様に、ポリエーテルサルホンフィルム上に
有機層/無機層/有機層/無機層の形成を行った。 （比較例３）実施例４と同様に、ポリエーテルサルホン
フィルム上に有機層/無機層/有機層/無機層の形成を行
ったが、本実施例では有機物層の厚みを2000nmとした。COMPARATIVE EXAMPLE 1 Instead of the tetrafunctional acrylate used in Example 1, a bifunctional neopentyl glycol diacrylate (NK ester A-NPG: new, having a volume shrinkage of 19.1% by a UV crosslinking reaction) was used. (Nakamura Chemical Co., Ltd.) was used to form an organic layer / inorganic layer / organic layer / inorganic layer on the polyethersulfone film in the same manner as in Example 1. (Comparative Example 2) Instead of the tetrafunctional acrylate used in Example 1, a bifunctional tripropylene glycol diacrylate (NK ester APG-200: Shin-Nakamura Chemical Co., Ltd.) having a volume shrinkage of 15.5% due to a UV crosslinking reaction. (Manufactured by Mfg. Co.) was used in the same manner as in Example 1 to form an organic layer / inorganic layer / organic layer / inorganic layer on the polyethersulfone film. Comparative Example 3 An organic layer / inorganic layer / organic layer / inorganic layer was formed on a polyethersulfone film in the same manner as in Example 4, but the thickness of the organic material layer was 2000 nm in this example.

【００１０】（評価）各フィルムの水蒸気透過度をJISK
7129B法にて測定した。また、30mmφの棒に１回巻きつ
けた後、再度水蒸気透過度をJISK7129B法にて測定し、
目視による外観と光学顕微鏡によるバリア膜クラックの
観察を行った。結果を表１に示す。(Evaluation) The water vapor transmission rate of each film is JIS K
It was measured by the 7129B method. Also, after wrapping around a 30 mmφ rod once, measure the water vapor permeability again by JIS K7129B method,
The appearance was visually observed and the cracks in the barrier film were observed with an optical microscope. The results are shown in Table 1.

【００１１】[0011]

【表１】 [Table 1]

【００１２】実施例１〜７においては、いずれの評価結
果も表示素子用としての要求特性を十分に満たしていた
が、有機層のＵＶ架橋反応による体積収縮率が大きい比
較例１、２では、実施例に比較して水蒸気透過度がやや
高い値となった。これは、架橋反応による反応収縮応力
により有機層と無機層との密着が低下したことや部分的
な無機バリア層の破壊が発生したことによるものと推定
される。また、曲げ処理によって、水蒸気透過とが大き
く増大した。これは有機層が局所的に破壊され、これに
より無機層に影響を及ぼしているものと考えられる。In each of Examples 1 to 7, all the evaluation results sufficiently satisfied the required characteristics for a display element, but in Comparative Examples 1 and 2 in which the organic layer has a large volume shrinkage due to the UV crosslinking reaction, The water vapor permeability was slightly higher than that of the example. It is presumed that this is because the reaction shrinkage stress due to the cross-linking reaction caused the adhesion between the organic layer and the inorganic layer to deteriorate, and the partial destruction of the inorganic barrier layer to occur. Also, the bending treatment significantly increased the water vapor transmission rate. It is considered that this is because the organic layer is locally destroyed, which affects the inorganic layer.

【００１３】[0013]

【発明の効果】本発明は、高いガスバリアをもつ透明フ
ィルムであり、しかも曲げることで水蒸気バリア性が低
下しないという特性を持つものである。本発明のフィル
ムをたとえば表示用素子として適用すれば、軽くて割れ
ないディスプレイが実現できる。また、薬品などの保存
に適用すれば中身が見えて、落としても割れないような
保存容器を実現することも可能であり、その工業的価値
は極めて高い。INDUSTRIAL APPLICABILITY The present invention is a transparent film having a high gas barrier and has a characteristic that the water vapor barrier property is not deteriorated by bending. When the film of the present invention is applied as a display element, for example, a light and non-breakable display can be realized. In addition, if it is applied to the storage of chemicals, it is possible to realize a storage container whose contents can be seen and does not break when dropped, and its industrial value is extremely high.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０８Ｆ 299/02 Ｃ０８Ｆ 299/02 Ｃ２３Ｃ 14/08 Ｃ２３Ｃ 14/08 Ｎ 14/20 14/20 14/24 14/24 Ｎ Ｆターム(参考） 4F100 AA00C AA00E AA12C AA12E AA20C AA20E AD05C AD05E AK01A AK02A AK25B AK25D AK25J AK55A AL01B AL01D AT00A BA03 BA04 BA05 BA08 BA10A BA10B BA10C BA10D BA10E BA13 EJ05B EJ05D EJ54 GB15 JA05A JA20B JA20D JD04 YY00A YY00B YY00D 4J011 CA01 CA08 4J027 AB36 AE10 AG36 AJ08 AJ09 BA07 BA17 BA19 BA20 BA24 BA26 BA27 BA28 BA29 CC03 CC05 CC06 4J100 AL02Q AL62P AL63P AL66P AL67P BA03P BA11P BC73P CA01 CA04 CA23 DA36 FA18 JA43 JA51 JA58 4K029 AA11 AA25 BA46 BA62 BB02 CA01 DB05 DB06 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) C08F 299/02 C08F 299/02 C23C 14/08 C23C 14/08 N 14/20 14/20 14/24 14 / 24 NF Term (Reference) 4F100 AA00C AA00E AA12C AA12E AA20C AA20E AD05C AD05E AK01A AK02A AK25B AK25D AK25J AK55A AL01B AL01J01 JA01A00 JA05A05J05A05B15BA05B05BA08B10BA10B10B10BBABBA10CBAABA 4J027 AB36 AE10 AG36 AJ08 AJ09 BA07 BA17 BA19 BA20 BA24 BA26 BA27 BA28 BA29 CC03 CC05 CC06 4J100 AL02Q AL62P AL63P AL66P AL67P BA03P BA11P BC73P CA01 CA04 CA23 DA36 FA18 JA43 JA51 JA58 4K029 AA11 DBB02 CA46 BA46

Claims (7)

【特許請求の範囲】[Claims] 【請求項１】 高分子材料からなる基材の少なくとも片
面に、真空製膜法により有機層と無機層とが交互に少な
くとも一層以上積層され、更に真空槽内で前記有機層を
架橋させることにより得られる水蒸気バリア性プラスチ
ックフィルムであり、前記有機層がアクリロイル基また
はメタクリロイル基を有するモノマーを架橋させて得ら
れる架橋反応による体積収縮率が１０％より小さい高分
子を主成分とすることを特徴とする水蒸気バリア性プラ
スチックフィルム。1. An organic layer and an inorganic layer are alternately laminated on at least one surface of a base material made of a polymer material by a vacuum film forming method, and the organic layer is crosslinked in a vacuum chamber. A water vapor barrier plastic film obtained, characterized in that the organic layer is mainly composed of a polymer having a volume shrinkage rate of less than 10% by a crosslinking reaction obtained by crosslinking a monomer having an acryloyl group or a methacryloyl group. Water vapor barrier plastic film. 【請求項２】 前記有機層が、２官能以上のアクリロイ
ル基またはメタクリロイル基を有する１種類以上のモノ
マー、または２官能以上のアクリロイル基またはメタク
リロイル基を有する１種類以上のモノマーと単官能以上
のアクリロイル基またはメタクリロイル基を有する1種
類以上のモノマーとの混合物を、架橋させて得られる高
分子を主成分とする請求項１記載の水蒸気バリア性プラ
スチックフィルム。2. The organic layer comprises one or more kinds of monomers having a bifunctional or higher functional acryloyl group or methacryloyl group, or one or more kinds of monomers having a bifunctional or higher functional acryloyl group or methacryloyl group and monofunctional or higher functional acryloyl. The water vapor barrier plastic film according to claim 1, which comprises a polymer obtained by crosslinking a mixture with one or more kinds of monomers having a group or a methacryloyl group as a main component. 【請求項３】 ２官能以上のアクリロイル基またはメタ
クリロイル基を有するモノマーが２官能以上のイソシア
ヌル酸アクリレートまたはエポキシアクリレートまたは
ウレタンアクリレートである請求項２記載の水蒸気バリ
ア性プラスチックフィルム。3. The water vapor barrier plastic film according to claim 2, wherein the monomer having a bifunctional or higher functional acryloyl group or a methacryloyl group is a bifunctional or higher functional isocyanuric acid acrylate, epoxy acrylate or urethane acrylate. 【請求項４】 前記有機層の厚みが１０〜１０００ｎｍ
である請求項１〜３いずれか１項記載の水蒸気バリア性
プラスチックフィルム。4. The organic layer has a thickness of 10 to 1000 nm.
The water vapor barrier plastic film according to any one of claims 1 to 3. 【請求項５】 前記無機層が珪素酸化物または珪素窒化
物または珪素窒化酸化物を主成分とする請求項１〜４い
ずれか１項記載の水蒸気バリア性プラスチックフィル
ム。5. The water vapor barrier plastic film according to claim 1, wherein the inorganic layer contains silicon oxide, silicon nitride, or silicon nitride oxide as a main component. 【請求項６】 前記基材のガラス転移温度が200℃以上
である請求項１〜５いずれか１項記載の水蒸気バリア性
プラスチックフィルム。6. The water vapor barrier plastic film according to claim 1, wherein the glass transition temperature of the substrate is 200 ° C. or higher. 【請求項７】 前記基材がノルボルネン系樹脂またはポ
リエーテルスルホンを主成分とする請求項１〜６いずれ
か１項記載の水蒸気バリア性プラスチックフィルム。7. The water vapor barrier plastic film according to claim 1, wherein the base material contains a norbornene-based resin or polyether sulfone as a main component.
JP2001243096A 2001-08-10 2001-08-10 Plastic film having water vapor barrier properties Pending JP2003053881A (en)

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