JP2005059211A - Gas barrier base material - Google Patents
Gas barrier base material Download PDFInfo
- Publication number
- JP2005059211A JP2005059211A JP2003196058A JP2003196058A JP2005059211A JP 2005059211 A JP2005059211 A JP 2005059211A JP 2003196058 A JP2003196058 A JP 2003196058A JP 2003196058 A JP2003196058 A JP 2003196058A JP 2005059211 A JP2005059211 A JP 2005059211A
- Authority
- JP
- Japan
- Prior art keywords
- gas barrier
- barrier layer
- base material
- inorganic
- inorganic gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 230000004888 barrier function Effects 0.000 title claims abstract description 180
- 239000000463 material Substances 0.000 title claims abstract description 42
- 229910001872 inorganic gas Inorganic materials 0.000 claims abstract description 75
- 229920005989 resin Polymers 0.000 claims abstract description 39
- 239000011347 resin Substances 0.000 claims abstract description 39
- 238000002844 melting Methods 0.000 claims abstract description 20
- 230000008018 melting Effects 0.000 claims abstract description 20
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- 238000010030 laminating Methods 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 85
- 239000010410 layer Substances 0.000 claims description 83
- 239000000758 substrate Substances 0.000 claims description 80
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 230000007797 corrosion Effects 0.000 claims description 29
- 238000005260 corrosion Methods 0.000 claims description 29
- 238000011156 evaluation Methods 0.000 claims description 20
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 10
- 229910052791 calcium Inorganic materials 0.000 claims description 10
- 239000011575 calcium Substances 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 230000005540 biological transmission Effects 0.000 claims description 8
- 230000009477 glass transition Effects 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 230000003746 surface roughness Effects 0.000 claims description 6
- 238000002441 X-ray diffraction Methods 0.000 claims description 4
- 239000011247 coating layer Substances 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 abstract description 9
- 239000003814 drug Substances 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 36
- 229910052751 metal Inorganic materials 0.000 description 18
- 239000002184 metal Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- 210000004027 cell Anatomy 0.000 description 12
- 239000004973 liquid crystal related substance Substances 0.000 description 9
- 230000035699 permeability Effects 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 238000005401 electroluminescence Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000004695 Polyether sulfone Substances 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229920006393 polyether sulfone Polymers 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 229910017107 AlOx Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910017947 MgOx Inorganic materials 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005477 sputtering target Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000005280 amorphization Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 210000002858 crystal cell Anatomy 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229920006241 epoxy vinyl ester resin Polymers 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 238000005224 laser annealing Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Laminated Bodies (AREA)
Abstract
Description
【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ガスバリア基材に関する。
【０００２】
【従来の技術】
従来から、樹脂基板やフィルムの表面にアルミニウムや酸化アルミニウム、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・水蒸気バリア性フィルムは、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樹脂等のフィルム基材が採用され始めている。また、樹脂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、透明樹脂等のフィルム基材はガラスに比べ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、酸素や水蒸気が浸透し、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材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板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樹脂フィルム上に酸化珪素を蒸着したもの（例えば、特許文献１参照。）酸化アルミニウムを蒸着したもの（例えば、特許文献２参照。）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例えば水蒸気の透過性で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ガス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。
【０００３】
ところが、ごく近年においてさらなるガス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、さらに高いガス・水蒸気バリア性、例えば水蒸気の透過性で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。
【０００４】
【特許文献１】
特開昭５３−１２９５３号公報
【特許文献２】
特開昭５８−２１７３４４号公報
【０００５】
【発明が解決しようとする課題】
本発明の目的は、従来よりも高いガスバリア性能を持つガスバリア基材を提供することにある。
【０００６】
【課題を解決するための手段】
すなわち本発明は、
（１）樹脂基材の少なくとも片面に無機ガスバリア層を積層したガスバリア基材であって、無機ガスバリア層の融点Ｔｍ（Ｋ）に対する無機ガスバリア層形成時の樹脂基材温度Ｔｓ（Ｋ）の比（Ｔｓ／Ｔｍ）が０．２５以上１．０未満であるガスバリア基材。
（２）樹脂基材上の少なくとも片面に無機ガスバリア層を積層したガスバリア基材であって、無機ガスバリア層の融点が１５００℃未満であるガスバリア基材。
（３）樹脂基材の少なくとも片面に無機ガスバリア層を積層したガスバリア基材であって、無機ガスバリア層の融点Ｔｍ（Ｋ）に対する無機ガスバリア層形成時の樹脂基材温度Ｔｓ（Ｋ）の比（Ｔｓ／Ｔｍ）が０．２５〜１．０であり、かつ、無機ガスバリア層の融点が１５００℃未満であるガスバリア基材。
・ （４）樹脂基材の少なくとも片面に無機ガスバリア層を積層したガスバリア基材であって、樹脂基材のガラス転移温度Ｔｇが２００℃以上である（１）〜（３）のガスバリア基材。
（５）Ｘ線回折測定で非晶であることを特徴とする（１）〜（４）のガスバリア基材。
（６）無機ガスバリア層成膜中あるいは成膜後に無機ガスバリア膜中の結晶部を非晶化する処理を行なった（５）のガスバリア基材。
（７）無機ガスバリア層の表面粗さ算術平均値（Ｒａ）が、２０μｍ×２０μｍ角の領域において、Ｒａ＜１０ｎｍ、最大高さ（Ｒｙ）がＲｙ＜０．３μｍであり、且つ平均線からの深さが１０ｎｍ以上で穴深さと穴直径のアスペクト比（穴深さ／穴直径）が０．２よりも大きい穴が無く、表面の最大高さと幅の最小値のアスペクト比（最大高さ／幅最小値）が０．２よりも大きい局所的な突起も無い（１）〜（６）のガスバリア基材。
（８）水蒸気透過速度が０．０１ｇ／ｍ２／ｄａｙより小さくかつ、酸素透過速度が０．１ｃｍ３／ｍ２／ｄａｙ／ａｔｍより小さい（１）〜（７）のガスバリア基材。
（９）カルシウムコロージョン評価において５０℃９５％ＲＨ恒温恒湿度１２時間処理後の、５０μｍ以上に成長する腐食が１ｍｍ２の範囲で５個以下かつ、腐食面積率１％以下である（１）〜（８）のガスバリア基材。
（１０）無機ガスバリア層の上面に有機物コート層を設けた（７）〜（９）のガスバリア基材。
（１１）無機ガスバリア層が２層以上である（１）〜（１０）のガスバリア基材。
（１２）（１）〜（１１）のガスバリア基材が透明であるガスバリア基材。
（１３）（１）〜（１２）のガスバリア基材を利用した表示デバイス用基板。
（１４）（１）〜（１２）のガスバリア基材を利用した表示デバイス。
である。
【０００７】
【発明の実施の形態】
本発明のガスバリア基材は、樹脂基材上に少なくとも片面に無機ガスバリア層を積層したガスバリア基材であって、この無機ガスバリア層が、無機ガスバリア層の融点Ｔｍ（Ｋ）に対する無機ガスバリア層形成時の樹脂基材温度Ｔｓ（Ｋ）の比（Ｔｓ／Ｔｍ）の値で０．２５以上１．０未満で形成されることを特徴とするガスバリア基材である。（Ｔｓ／Ｔｍ）の値が０．２５未満であると、粗な構造の膜になったりして、優れたガスバリア特性を得ることが難しい。また、（Ｔｓ／Ｔｍ）の値が１．０以上であると、樹脂基材がこの温度に耐えられないことが多いため、現実的ではない。さらに好ましくは、（Ｔｓ／Ｔｍ）の値が０．３５以上１．０未満である。
【０００８】
本発明のガスバリア基材は、樹脂基材上の少なくとも片面に無機ガスバリア層を積層したガスバリア基材であって、この無機ガスバリア層の融点が１５００℃未満であることを特徴とするガスバリア基材であってもよい。樹脂基材上に無機ガスバリア層を形成する場合、この無機ガスバリア層の融点が１５００℃以上であると、粗な構造の膜になり、優れたガスバリア特性を得ることが難しい。
【０００９】
本発明のガスバリア基材の無機ガスバリア層の形成には、熱蒸発法、スパッタリング法、イオンプレーティング法、クラスターイオンビーム法などの物理的方法や、ＣＶＤ法などの化学的方法を用いることができる。
【００１０】
本発明のガスバリア基材上に積層された無機ガスバリア層の融点Ｔｍは、無機ガスバリア層の化学組成分析を行い、組成を確認した後、これと同組成の材料を混合、溶融、固化
させたあと、この材料の融点を測定するなどの方法で求めることができる。ただし、かかる組成の無機ガスバリア層に対応した材料を徐冷しても結晶性が得られない場合、融点Ｔｍの替わりにこの材料のガラス転移温度ＴｇをＴｍとする。また、無機ガスバリア層形成時の樹脂基材温度Ｔｓは、ガスバリア基材の無機ガスバリア層形成面と反対側に温度測定用ステッカーを着けるなどの方法で測定することもできる。ただし、ガスバリア基材が無機ガスバリア層形成時よりも成膜装置中で高温にさらされる可能性のある場合、ガスバリア基材の無機ガスバリア層形成面と反対側に熱伝対を接触させて測定するなどの方法も用いることができる。また、赤外センサーのような非接触式温度計で、温度をモニタリングしても良い。
【００１１】
本発明のガスバリア基材は、樹脂基材のガラス転移温度Ｔｇが２００℃以上であることが好ましい。ガラス転移温度Ｔｇ２００℃以上の樹脂基材としては、ポリエーテルサルフォン樹脂（ＰＥＳ）、エポキシ樹脂、ビニルエステル樹脂などを使用することができる。
【００１２】
本発明のガスバリア基材は、非晶であることが好ましい。このため、無機ガスバリア層の原材料となる無機化合物は、ガラス形成能が高い金属酸化物、複合酸化物などを用いることもできる。例えば、ＳｉＯ２−Ｂ２Ｏ３，ＳｉＯ２−ＺｎＯなどを用いることができる。また、ガスバリア層成膜中あるいは成膜後に無機ガスバリア膜中の結晶部を非晶化してもよい。非晶であるか否かの判定はＸ線回折測定で、行うことができ、非晶化処理工程には、レーザーアニール法、電子線照射、イオンビーム照射などを用いることもできる。
【００１３】
本発明のガスバリア基材は、無機ガスバリア層表面が、２０μｍ×２０μｍ角の領域において、その表面粗さ算術平均値（Ｒａ）がＲａ＜１０ｎｍ、最大高さ（Ｒｙ）がＲｙ＜０．３μｍであり、且つ平均線からの深さが１０ｎｍ以上で穴深さと穴直径のアスペクト比（穴深さ／穴直径）が０．２よりも大きい穴の無く、表面の最大高さと幅の最小値のアスペクト比（最大高さ／幅最小値）が０．２よりも大きい局所的な突起も無いことが好ましい。これは表面平滑性が悪化すると、積層する無機ガスバリア膜にクラックや穴状欠陥が発生し易くなり、フィルム自体のバリア性能を低下させることも考えられる。
【００１４】
本発明のガスバリア基材は、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高バリア性が要求される用途に使用するためには、このガスバリア基材において、水蒸気透過速度が０．０１ｇ／ｍ２／ｄａｙより小さくかつ、酸素透過速度が０．１ｃｍ３／ｍ２／ｄａｙ／ａｔｍより小さいことが好ましい。また、これら高バリア性が要求される用途に使用するためには、カルシウムコロージョン評価において５０℃９５％ＲＨ恒温恒湿度処理後の、５０μｍ以上に成長する腐食が１ｍｍ２の範囲で５個以下かつ、腐食面積率１％以下であることが好ましい。ここでいうカルシウムコロージョン評価とは、「（１）水蒸気バリア性を評価するフィルムシートの片面に、水分と反応して腐食する金属層を真空プロセスにて形成させた後、水蒸気不透過性金属層でこの面を封止した水蒸気バリア性評価用セル、又は、（２）前記水分と反応して腐食する金属層の厚さが３０ｎｍ〜５００ｎｍである請求項１記載の水蒸気バリア性評価用セル、又は、（３）前記水蒸気不透過性金属層の厚さが５００ｎｍ〜２０μｍである（１）又は（２）記載の水蒸気バリア性評価用セル、又は、（４）前記水蒸気不透過性金属層の表面粗さが、算術平均値（Ｒａ）でＲａ＜２０ｎｍ、最大高さ及び最大深さで最大高さ＜６００ｎｍ及び最大深さ＜２００ｎｍ、である（１）〜（３）記載の水蒸気バリア性評価用セル、又は、（５）前記水分と反応して腐食する金属層の厚さ（ａ）に対する水蒸気不透過性金属層の厚さ（ｂ）の比、すなわち、（ｂ）／（ａ）が２以上である（１）〜（４）記載の水蒸気バリア性評価用セル、又は、（６）前記水蒸気不透過性金属層の上層に、温度４０±０．５℃、相対湿度９０±２％の条件下に暴露したときにその質量変化が、暴露面積５０ｃｍ２で１ｍｇ／２４時間以下の有機物で密閉した（１）〜（５）記載の水蒸気バリア性評価用セル、又は、（７）前記水分と反応して腐食する金属層の材質にカルシウムを含む（１）〜（６）記載の水蒸気バリア性評価用セル、又は、（８）前記水蒸気不透過性金属層の材質にアルミニウム、亜鉛、錫、インジウム、鉛、銀、銅の何れかを含む（１）〜（７）記載の水蒸気バリア性評価用セル、又は、（９）前記水蒸気不透過性金属層が異なる材質の多層構造である（１）〜（８）記載の水蒸気バリア性評価用セル、又は、（１０）前記水蒸気不透過性金属層の材質が２種類以上の金属の合金である（１）〜（９）記載の水蒸気バリア性評価用セル、を用い（１１）任意の条件で恒温恒湿度処理を行ったあと、水分と反応して腐食する金属の腐食状態を観察する水蒸気バリア性評価方法、及び（１２）（１１）記載の水蒸気バリア性評価後に、セルからフィルムシートを、非破壊に取り外し、洗浄後、水分と反応して腐食した金属の腐食中心部分に対応するフィルムシート表面を、直接観察することにより、基材の欠陥部分の状態を評価する水蒸気バリア性評価方法、及び（１３）恒温恒湿度処理を行ったあと、水分と反応して腐食する金属の腐食面積と腐食金属の厚みから算出される金属腐食物の体積から、金属と反応する水分量を定量的に評価する水蒸気バリア性評価方法。」である。本発明では、ガスバリア基材をフィルムシートとしてカルシウムコロージョン評価を実施した。
【００１５】
本発明のガスバリア基材は、無機ガスバリア層の上に有機物コート層を設けてもよく、有機物コート層を設けることにより、ハンドリングや工程中での無機ガスバリア層へのダメージを防ぐ効果などが期待できる。
【００１６】
本発明のガスバリア基材は、樹脂基材上の片面あるいは両面に合計２層以上の無機ガスバリア層を積層してもよく、無機ガスバリア層を複数積層することにより、ガスバリア性がさらに向上することが期待できる。無機ガスバリア層を複数積層する仕方は、無機ガスバリア層を連続で複数層重ねても、間に有機層を挟んで積層してもよい。
【００１７】
本発明のガスバリア基材は、透明であることが好ましい。光を透過することにより、ディスプレイ基板、透明性が要求される包装用途等にも好適に用いることができる。ここで、透明な材料とは、４００ｎｍ〜７００ｎｍの任意の波長領域の光線を６０％以上透過することが好ましく、さらに好ましくは７０％以上の透過であり、最も好ましくは８０％以上の透過である。
【００１８】
本発明のガスバリア基材は、液晶、有機ＥＬなどの表示デバイス用途に用いることができる。
【００１９】
【実施例】
以下、実施例により本発明を具体的に説明するが、本発明はこの実施例によって限定されるものではない。
（実施例１）
ポリエーテルサルホンフィルム樹脂基材（ガラス転移温度Ｔｇ＝２２３℃）に２官能のエポキシアクリレート２５ｗｔ％、ジエチレングリコール４８．５ｗｔ％、酢酸エチル２４ｗｔ％、シランカップリング剤１ｗｔ％、光開始剤１．５ｗｔ％からなる均一な混合溶液をスピンコーターで塗布し、８０℃１０分加熱乾燥後さらにＵＶ照射で硬化させて２μｍの樹脂層を形成した。つぎに、ＲＦマグネトロンスパッタ装置を用い、この真空槽内に前記有機物層を形成したフィルムをセットし１０−４Ｐａ台まで真空引きし、放電ガスとしてアルゴンを分圧で０．５Ｐａ導入した。雰囲気圧力が安定したところで放電を開始し、スパッタリングターゲットである無アルカリガラス上に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無機ガスバリア層の形成を開始した。無機ガスバリア層形成時の樹脂基材温度Ｔｓ（Ｋ）は、４５０（Ｋ）であった。５０ｎｍの膜が堆積したところでシャッターを閉じて成膜を終了した。真空槽内に大気を導入し無機ガスバリア層の形成されたフィルムを取り出した。この条件で成膜した無機ガスバリア層の元素濃度をＸ線光電子分光分析（ＥＳＣＡ）で測定したところそのｍｏｌ％は、「ＳｉＯｘ ５０％， ＣａＯｘ ４％， ＡｌＯｘ １６％， ＮａＯｘ ５％， ＭｇＯｘ １３％， ＢＯｘ １０％， その他 ２％」であった。また、この無機ガスバリア層はＸ線回折測定の結果（非晶）であることが確認された。「ＳｉＯｘ ５０％， ＣａＯｘ ４％， ＡｌＯｘ １６％， ＮａＯｘ ５％， ＭｇＯｘ １３％， ＢＯｘ １０％， その他 ２％」の組成で、原料を混合、溶融、冷却により、無機ガスバリア層と同組成のガラスを作製し、このガラス転移温度を測定したところ、１０８０（Ｋ）であった。従って、この無機ガスバリア層の融点Ｔｍ（Ｋ）に対する無機ガスバリア層形成時の樹脂基材温度Ｔｓ（Ｋ）の比（Ｔｓ／Ｔｍ）は、０．４２である。
【００２０】
この無機ガスバリア層表面をＡＦＭ観察した結果、の表面粗さ算術平均値（Ｒａ）が、２０μｍ×２０μｍ角の領域で、Ｒａ＝１．１（ｎｍ）、最大高さＲｙ＝３０．９（ｎｍ）、平均線から１０（ｎｍ）以上の深さの穴は認められなかった。
【００２１】
このガスバリア基材の水蒸気透過度をＪＩＳ Ｋ ７１２９ Ｂ法にて測定した結果、水蒸気透過度は０．０１ｇ／ｍ２／ｄａｙより小さくなった。
【００２２】
このガスバリア基材の酸素透過度をＪＩＳ Ｋ ７１２６ Ｂ法にて測定した結果、酸素透過度は０．１ｃｍ３／ｍ２／ｄａｙ／ａｔｍより小さくなった。
【００２３】
また、カルシウムコロージョン評価において５０℃９５％ＲＨ恒温恒湿度１２時間処理後の、５０μｍ以上に成長する腐食が１ｍｍ２の範囲で０．９個（測定数２０の平均）、腐食面積率０．４％であった。
【００２４】
（比較例１）
ポリエーテルサルホンフィルム樹脂基材（ガラス転移温度Ｔｇ＝２２３℃）に２官能のエポキシアクリレート（昭和高分子：ＶＲ−６０−ＬＡＶ）２５ｗｔ％、ジエチレングリコール４８．５ｗｔ％、酢酸エチル２４ｗｔ％、シランカップリング剤１ｗｔ％、光開始剤１．５ｗｔ％からなる均一な混合溶液をスピンコーターで塗布し、８０℃１０分加熱乾燥後さらにＵＶ照射で硬化させて２μｍの樹脂層を形成した。つぎに、ＲＦマグネトロンスパッタ装置を用い、この真空槽内に前記有機物層を形成したフィルムをセットし１０−４Ｐａ台まで真空引きし、放電ガスとしてアルゴンを分圧で０．５Ｐａ導入した。雰囲気圧力が安定したところで放電を開始し、スパッタリングターゲットであるＳｉＯ２上に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無機ガスバリア層の形成を開始した。無機ガスバリア層形成時の樹脂基材温度Ｔｓ（Ｋ）は、４５０（Ｋ）であった。５０ｎｍの膜が堆積したところでシャッターを閉じて成膜を終了した。真空槽内に大気を導入し無機ガスバリア層の形成されたフィルムを取り出した。ＳｉＯ２のＴｍは２００３（Ｋ）である。従って、この無機ガスバリア層の融点Ｔｍ（Ｋ）に対する無機ガスバリア層形成時の樹脂基材温度Ｔｓ（Ｋ）の比（Ｔｓ／Ｔｍ）は、０．２２である。
【００２５】
この無機ガスバリア層表面をＡＦＭ観察した結果、の表面粗さ算術平均値（Ｒａ）が、２０μｍ×２０μｍ角の領域で、Ｒａ＝１．２（ｎｍ）、最大高さＲｙ＝１９．９（ｎｍ）、平均線から１０（ｎｍ）以上の深さの穴は認められなかった。
【００２６】
このガスバリア基材の水蒸気透過度をＪＩＳ Ｋ ７１２９ Ｂ法にて測定した結果、水蒸気透過度は０．０３ｇ／ｍ２／ｄａｙであった。
【００２７】
このガスバリア基材の酸素透過度をＪＩＳ Ｋ ７１２６ Ｂ法にて測定した結果、酸素透過度は０．１ｃｍ３／ｍ２／ｄａｙ／ａｔｍより小さくなった。
【００２８】
また、カルシウムコロージョン評価において５０℃９５％ＲＨ恒温恒湿度１２時間処理後の、５０μｍ以上に成長する腐食が１ｍｍ２の範囲で６．１個（測定数２０の平均）、腐食面積率１．２％であった。
【００２９】
前記実施例と比較例でのカルシウムコロージョン評価における腐食数および腐食面積は、実施例におけるガスバリア性能が飛躍的に向上したことを示している。ガスバリア基材を表示デバイス用途としたとき、ガスバリア性能の向上すなわちカルシウムコロージョン評価における腐食数、腐食面積が少ないほど表示品質、耐久性能が向上する。
【００３０】
【発明の効果】
本発明により、従来よりも高いガスバリア性能を持つガスバリア基材を提供すること。
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ガスバリア基材を提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a gas barrier substrate that can be applied to a wide range of uses such as an optical member, an electronic member, a general packaging member, and a chemical packaging member.
[0002]
[Prior art]
Conventionally, a gas / water vapor barrier film in which a metal oxide thin film such as aluminum, aluminum oxide, magnesium oxide, silicon oxide or the like is formed on the surface of a resin substrate or film is used to wrap articles and foods that require gas blocking. It is widely used in packaging applications to prevent the alteration of industrial products and pharmaceuticals. Moreover, it is used with a liquid crystal display element, a solar cell, an electroluminescence (EL) substrate, etc. besides the packaging use. In particular, transparent substrates that have been applied to liquid crystal display elements, EL elements, etc. have recently been required to be lighter and larger, have long-term reliability and a high degree of freedom in shape, and can display curved surfaces. With the addition of high demands such as being, film base materials such as transparent resins have begun to be used in place of glass substrates that are heavy, fragile and difficult to increase in area. In addition, the resin film not only satisfies the above requirements, but also has a roll-to-roll method, so that it has higher productivity than glass and is advantageous in terms of cost reduction. However, a film substrate such as a transparent resin has a problem that gas barrier properties are inferior to glass. If a base material with inferior gas barrier properties is used, oxygen and water vapor will permeate, causing deterioration of the liquid crystal in the liquid crystal cell, for example, resulting in display defects and deterioration of display quality. 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 material or a liquid crystal display element, a film obtained by vapor-depositing silicon oxide on a resin film (for example, see Patent Document 1) or a film obtained by vapor-depositing aluminum oxide (for example, see Patent Document 2). All of them have a water vapor barrier property of about 1 g / m 2 / day. In recent years, the demand for gas barrier performance to a film substrate, for example, about 0.1 g / m 2 / day in terms of water vapor permeability has increased due to the development of large-sized liquid crystal displays and high-definition displays. In order to meet this demand, film formation by sputtering or CVD has been studied as a means for expecting higher gas barrier performance.
[0003]
However, in recent years, development of organic EL displays and high-definition color liquid crystal displays that require further gas barrier properties has progressed, and while maintaining the transparency that can be used therefor, even higher gas / water vapor barrier properties such as water vapor There has been a demand for substrates that are permeable and have a performance of less than 0.1 g / m 2 / day.
[0004]
[Patent Document 1]
JP-A-53-12953 [Patent Document 2]
Japanese Patent Laid-Open No. 58-217344
[Problems to be solved by the invention]
An object of the present invention is to provide a gas barrier substrate having higher gas barrier performance than before.
[0006]
[Means for Solving the Problems]
That is, the present invention
(1) A gas barrier substrate in which an inorganic gas barrier layer is laminated on at least one surface of a resin substrate, and the resin substrate temperature T s (K) at the time of forming the inorganic gas barrier layer with respect to the melting point T m (K) of the inorganic gas barrier layer A gas barrier substrate having a ratio (T s / T m ) of 0.25 or more and less than 1.0.
(2) A gas barrier base material in which an inorganic gas barrier layer is laminated on at least one surface on a resin base material, wherein the inorganic gas barrier layer has a melting point of less than 1500 ° C.
(3) A gas barrier substrate in which an inorganic gas barrier layer is laminated on at least one surface of a resin substrate, and the resin substrate temperature T s (K) at the time of forming the inorganic gas barrier layer with respect to the melting point T m (K) of the inorganic gas barrier layer A gas barrier substrate having a ratio (T s / T m ) of 0.25 to 1.0 and an inorganic gas barrier layer having a melting point of less than 1500 ° C.
- (4) A gas barrier base material formed by laminating at least one side inorganic gas barrier layer of the resin substrate, gas barrier groups glass transition temperature T g of the resin substrate is 200 ° C. or higher (1) to (3) material .
(5) The gas barrier substrate according to (1) to (4), wherein the gas barrier substrate is amorphous by X-ray diffraction measurement.
(6) The gas barrier substrate according to (5), wherein a treatment for amorphizing a crystal portion in the inorganic gas barrier film is performed during or after the formation of the inorganic gas barrier layer.
(7) In the region where the surface roughness arithmetic average value (Ra) of the inorganic gas barrier layer is 20 μm × 20 μm square, Ra <10 nm, the maximum height (Ry) is Ry <0.3 μm, and from the average line There is no hole with a depth of 10 nm or more and the aspect ratio of the hole depth to the hole diameter (hole depth / hole diameter) is larger than 0.2, and the aspect ratio (maximum height / The gas barrier base material according to any one of (1) to (6), wherein there is no local protrusion having a minimum width (greater than 0.2).
(8) A gas barrier substrate having a water vapor transmission rate lower than 0.01 g / m 2 / day and an oxygen transmission rate lower than 0.1 cm 3 / m 2 / day / atm (1) to (7).
(9) In calcium corrosion evaluation, the corrosion that grows to 50 μm or more after treatment at 50 ° C. and 95% RH constant temperature and humidity for 12 hours is 5 or less in a range of 1 mm 2 and the corrosion area ratio is 1% or less (1) to (8) Gas barrier base material.
(10) The gas barrier substrate according to (7) to (9), wherein an organic coating layer is provided on the upper surface of the inorganic gas barrier layer.
(11) The gas barrier substrate according to (1) to (10), wherein the inorganic gas barrier layer has two or more layers.
(12) A gas barrier substrate in which the gas barrier substrate of (1) to (11) is transparent.
(13) A display device substrate using the gas barrier base material of (1) to (12).
(14) A display device using the gas barrier substrate according to (1) to (12).
It is.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The gas barrier substrate of the present invention is a gas barrier substrate in which an inorganic gas barrier layer is laminated on at least one surface on a resin substrate, and this inorganic gas barrier layer forms an inorganic gas barrier layer with respect to the melting point T m (K) of the inorganic gas barrier layer. It is a gas barrier substrate characterized by being formed at a value of the ratio (T s / T m ) of the resin substrate temperature T s (K) at the time of 0.25 or more and less than 1.0. When the value of (T s / T m ) is less than 0.25, a film having a rough structure is formed, and it is difficult to obtain excellent gas barrier characteristics. In addition, if the value of (T s / T m ) is 1.0 or more, the resin base material often cannot withstand this temperature, which is not realistic. More preferably, the value of (T s / T m ) is 0.35 or more and less than 1.0.
[0008]
The gas barrier substrate of the present invention is a gas barrier substrate in which an inorganic gas barrier layer is laminated on at least one surface on a resin substrate, and the melting point of the inorganic gas barrier layer is less than 1500 ° C. There may be. When an inorganic gas barrier layer is formed on a resin substrate, if the melting point of the inorganic gas barrier layer is 1500 ° C. or higher, a film having a rough structure is formed, and it is difficult to obtain excellent gas barrier characteristics.
[0009]
For the formation of the inorganic gas barrier layer of the gas barrier substrate of the present invention, a physical method such as a thermal evaporation method, a sputtering method, an ion plating method, a cluster ion beam method, or a chemical method such as a CVD method can be used. .
[0010]
The melting point Tm of the inorganic gas barrier layer laminated on the gas barrier substrate of the present invention was determined by conducting a chemical composition analysis of the inorganic gas barrier layer, confirming the composition, and then mixing, melting, and solidifying materials having the same composition. Then, it can be determined by a method such as measuring the melting point of this material. However, if the crystallinity is also gradually cooled materials corresponding to the inorganic gas barrier layer of such a composition can not be obtained, the glass transition temperature T g of the the material in place of the melting point T m and T m. The inorganic gas barrier layer-forming resin substrate temperature T s at the time can also be measured by a method such as wear stickers for temperature measurement on the opposite side of the inorganic gas barrier layer-forming surface of the gas barrier base. However, when there is a possibility that the gas barrier substrate is exposed to a higher temperature in the film forming apparatus than when the inorganic gas barrier layer is formed, measurement is performed by bringing a thermocouple in contact with the opposite side of the gas barrier substrate to the inorganic gas barrier layer forming surface. Such a method can also be used. Further, the temperature may be monitored with a non-contact type thermometer such as an infrared sensor.
[0011]
Gas barrier base material of the present invention preferably has a glass transition temperature T g of the resin substrate is 200 ° C. or higher. As the resin base material having a glass transition temperature Tg of 200 ° C. or higher, polyethersulfone resin (PES), epoxy resin, vinyl ester resin and the like can be used.
[0012]
The gas barrier substrate of the present invention is preferably amorphous. For this reason, a metal oxide, composite oxide, etc. with high glass formation ability can also be used for the inorganic compound used as the raw material of the inorganic gas barrier layer. For example, SiO 2 —B 2 O 3 , SiO 2 —ZnO, or the like can be used. Further, the crystal part in the inorganic gas barrier film may be amorphized during or after the gas barrier layer is formed. Whether the material is amorphous or not can be determined by X-ray diffraction measurement. Laser annealing, electron beam irradiation, ion beam irradiation, or the like can also be used for the amorphization treatment step.
[0013]
In the gas barrier substrate of the present invention, when the surface of the inorganic gas barrier layer is 20 μm × 20 μm square, the surface roughness arithmetic average value (Ra) is Ra <10 nm and the maximum height (Ry) is Ry <0.3 μm. There is no hole with an aspect ratio (hole depth / hole diameter) greater than 0.2 with a depth from the average line of 10 nm or more and a hole depth / hole diameter ratio of more than 0.2. It is preferable that there are no local protrusions having an aspect ratio (maximum height / minimum width) greater than 0.2. If surface smoothness deteriorates, cracks and hole-like defects are likely to occur in the laminated inorganic gas barrier film, and the barrier performance of the film itself may be reduced.
[0014]
The gas barrier substrate of the present invention has a water vapor transmission rate of 0.01 g / m 2 in order to be used for applications requiring high barrier properties such as organic EL displays and high-definition color liquid crystal displays. It is preferably smaller than / day and the oxygen transmission rate is smaller than 0.1 cm 3 / m 2 / day / atm. In addition, for use in applications requiring these high barrier properties, the corrosion that grows to 50 μm or more after the 50 ° C. and 95% RH constant temperature and humidity treatment in the calcium corrosion evaluation is 5 or less in the range of 1 mm 2 and The corrosion area ratio is preferably 1% or less. The calcium corrosion evaluation here refers to “(1) a metal layer that reacts with water and corrodes on one side of a film sheet for evaluating water vapor barrier properties by a vacuum process, and then a water vapor impermeable metal layer. The cell for evaluating water vapor barrier properties in which this surface is sealed, or (2) the cell for evaluating water vapor barrier properties according to claim 1, wherein the thickness of the metal layer that reacts with water and corrodes is 30 nm to 500 nm. Or (3) the cell for evaluating water vapor barrier properties according to (1) or (2), wherein the thickness of the water vapor impermeable metal layer is 500 nm to 20 μm, or (4) of the water vapor impermeable metal layer. Water vapor barrier properties according to (1) to (3), wherein the surface roughness is Ra <20 nm in arithmetic mean value (Ra), maximum height <600 nm and maximum depth <200 nm in maximum height and depth. Evaluation cell or (5) The ratio of the thickness (b) of the water vapor impermeable metal layer to the thickness (a) of the metal layer that reacts with water and corrodes, that is, (b) / (a) is 2 or more. (1)-(4) water vapor barrier evaluation cell, or (6) an upper layer of the water vapor impermeable metal layer, at a temperature of 40 ± 0.5 ° C. and a relative humidity of 90 ± 2%. When exposed, the change in mass of the water vapor barrier property evaluation cell according to (1) to (5) sealed with an organic substance of 1 mg / 24 hours or less at an exposed area of 50 cm 2 , or (7) reacts with the moisture. (1) to (6) the water vapor barrier property evaluation cell containing calcium in the material of the corroding metal layer, or (8) aluminum, zinc, tin, indium as the material of the water vapor impermeable metal layer, Water vapor barrier property evaluation according to any one of (1) to (7), including any of lead, silver, and copper A cell, or (9) a water vapor barrier evaluation cell according to (1) to (8), or (10) the water vapor impermeable metal layer, wherein the water vapor impermeable metal layer has a multilayer structure of different materials. (11) Using the water vapor barrier evaluation cell according to (1) to (9), wherein the material is an alloy of two or more kinds of metals. (11) After performing a constant temperature and humidity treatment under arbitrary conditions, it reacts with moisture. After the water vapor barrier property evaluation method for observing the corrosion state of the corroding metal and the water vapor barrier property evaluation according to (12) and (11), the film sheet is removed from the cell nondestructively, washed, and reacted with moisture. After performing the water vapor barrier property evaluation method for evaluating the state of the defective portion of the base material by directly observing the film sheet surface corresponding to the corroded center portion of the corroded metal, and (13) after performing the constant temperature and humidity treatment, Reacts with moisture From the volume of metal corrosion was calculated from the corrosion area and the thickness of the corrosion metal as corrosion, water vapor barrier property evaluation method for quantitatively evaluating the amount of water which reacts with the metal. It is. In the present invention, calcium corrosion evaluation was performed using a gas barrier substrate as a film sheet.
[0015]
The gas barrier substrate of the present invention may be provided with an organic coating layer on the inorganic gas barrier layer. By providing the organic coating layer, an effect of preventing damage to the inorganic gas barrier layer during handling or the process can be expected. .
[0016]
In the gas barrier substrate of the present invention, a total of two or more inorganic gas barrier layers may be laminated on one side or both sides of the resin substrate, and by laminating a plurality of inorganic gas barrier layers, the gas barrier property can be further improved. I can expect. As a method of laminating a plurality of inorganic gas barrier layers, a plurality of inorganic gas barrier layers may be laminated one after another, or may be laminated with an organic layer interposed therebetween.
[0017]
The gas barrier substrate of the present invention is preferably transparent. By transmitting light, it can be suitably used for display substrates and packaging applications that require transparency. Here, the transparent material preferably transmits 60% or more of light in an arbitrary wavelength region of 400 nm to 700 nm, more preferably 70% or more, and most preferably 80% or more. .
[0018]
The gas barrier substrate of the present invention can be used for display device applications such as liquid crystal and organic EL.
[0019]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by this Example.
(Example 1)
Polyether sulfone film resin base material (glass transition temperature Tg = 223 ° C.), bifunctional epoxy acrylate 25 wt%, diethylene glycol 48.5 wt%, ethyl acetate 24 wt%, silane coupling agent 1 wt%, photoinitiator 1.5 wt A uniform mixed solution consisting of% was applied with a spin coater, dried by heating at 80 ° C. for 10 minutes, and further cured by UV irradiation to form a 2 μm resin layer. Next, using an RF magnetron sputtering apparatus, the film on which the organic layer was formed was set in this vacuum chamber, evacuated to a level of 10 −4 Pa, and argon was introduced as a discharge gas at a partial pressure of 0.5 Pa. When the atmospheric pressure was stabilized, discharge was started, plasma was generated on the alkali-free glass as a sputtering target, and the sputtering process was started. When the process was stabilized, the shutter was opened and formation of an inorganic gas barrier layer on the film was started. The resin base material temperature T s (K) when forming the inorganic gas barrier layer was 450 (K). When the 50 nm film was deposited, the shutter was closed to complete the film formation. Air was introduced into the vacuum chamber, and the film on which the inorganic gas barrier layer was formed was taken out. When the element concentration of the inorganic gas barrier layer formed under these conditions was measured by X-ray photoelectron spectroscopy (ESCA), the mol% was “SiOx 50%, CaOx 4%, AlOx 16%, NaOx 5%, MgOx 13%. , BOx 10%, other 2% ”. Moreover, it was confirmed that this inorganic gas barrier layer was a result of the X-ray diffraction measurement (amorphous). Glass with the same composition as the inorganic gas barrier layer by mixing, melting and cooling the raw materials with the composition of “SiOx 50%, CaOx 4%, AlOx 16%, NaOx 5%, MgOx 13%, BOx 10%, and other 2%” When this glass transition temperature was measured, it was 1080 (K). Therefore, the ratio (T s / T m ) of the resin base material temperature T s (K) when forming the inorganic gas barrier layer to the melting point T m (K) of the inorganic gas barrier layer is 0.42.
[0020]
As a result of AFM observation of the surface of the inorganic gas barrier layer, Ra = 1.1 (nm) and maximum height Ry = 30.9 (nm) in a region where the surface roughness arithmetic average value (Ra) is 20 μm × 20 μm square. ) No holes having a depth of 10 nm or more from the average line were observed.
[0021]
As a result of measuring the water vapor permeability of this gas barrier substrate by the JIS K 7129 B method, the water vapor permeability was less than 0.01 g / m 2 / day.
[0022]
As a result of measuring the oxygen permeability of this gas barrier substrate by the JIS K 7126 B method, the oxygen permeability was smaller than 0.1 cm 3 / m 2 / day / atm.
[0023]
Further, in the calcium corrosion evaluation, after corrosion treatment at 50 ° C. and 95% RH constant temperature and humidity for 12 hours, 0.9 corrosion (average of 20 measurements) in the range of 1 mm 2 and corrosion area ratio of 0.4 %Met.
[0024]
(Comparative Example 1)
Polyether sulfone film resin substrate (glass transition temperature Tg = 223 ° C.), bifunctional epoxy acrylate (Showa Polymer: VR-60-LAV) 25 wt%, diethylene glycol 48.5 wt%, ethyl acetate 24 wt%, silane cup A uniform mixed solution consisting of 1 wt% ring agent and 1.5 wt% photoinitiator was applied by a spin coater, dried by heating at 80 ° C. for 10 minutes, and further cured by UV irradiation to form a 2 μm resin layer. Next, using an RF magnetron sputtering apparatus, the film on which the organic layer was formed was set in this vacuum chamber, evacuated to a level of 10 −4 Pa, and 0.5 Pa was introduced as a discharge gas at a partial pressure of 0.5 Pa. When the atmospheric pressure was stabilized, discharge was started, plasma was generated on SiO 2 as a sputtering target, and a sputtering process was started. When the process was stabilized, the shutter was opened and formation of an inorganic gas barrier layer on the film was started. The resin base material temperature T s (K) when forming the inorganic gas barrier layer was 450 (K). When the 50 nm film was deposited, the shutter was closed to complete the film formation. Air was introduced into the vacuum chamber, and the film on which the inorganic gas barrier layer was formed was taken out. The T m of SiO 2 is 2003 (K). Therefore, the ratio (T s / T m ) of the resin base material temperature T s (K) when forming the inorganic gas barrier layer to the melting point T m (K) of the inorganic gas barrier layer is 0.22.
[0025]
As a result of AFM observation of the surface of the inorganic gas barrier layer, Ra = 1.2 (nm) and maximum height Ry = 19.9 (nm) when the surface roughness arithmetic average value (Ra) is 20 μm × 20 μm square. ) No holes having a depth of 10 nm or more from the average line were observed.
[0026]
As a result of measuring the water vapor transmission rate of this gas barrier substrate by the JIS K 7129 B method, the water vapor transmission rate was 0.03 g / m 2 / day.
[0027]
As a result of measuring the oxygen permeability of this gas barrier substrate by the JIS K 7126 B method, the oxygen permeability was smaller than 0.1 cm 3 / m 2 / day / atm.
[0028]
Further, in the calcium corrosion evaluation, after the treatment at 50 ° C. and 95% RH, constant temperature and humidity for 12 hours, 6.1 pieces of corrosion growing to 50 μm or more in the range of 1 mm 2 (average of 20 measurements), corrosion area ratio 1.2 %Met.
[0029]
The number of corrosion and the corrosion area in the calcium corrosion evaluation in the examples and comparative examples indicate that the gas barrier performance in the examples has been dramatically improved. When the gas barrier substrate is used as a display device, the display quality and durability are improved as the gas barrier performance is improved, that is, the number of corrosion and the corrosion area in the calcium corrosion evaluation are smaller.
[0030]
【The invention's effect】
According to the present invention, a gas barrier substrate having higher gas barrier performance than the conventional one is provided.
A gas barrier substrate that can be applied to a wide range of applications such as optical members, electronics members, general packaging members, and medicine packaging members can be provided.
Claims (14)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003196058A JP2005059211A (en) | 2003-06-16 | 2003-07-11 | Gas barrier base material |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003170243 | 2003-06-16 | ||
| JP2003196058A JP2005059211A (en) | 2003-06-16 | 2003-07-11 | Gas barrier base material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005059211A true JP2005059211A (en) | 2005-03-10 |
| JP2005059211A5 JP2005059211A5 (en) | 2007-05-17 |
Family
ID=34379708
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003196058A Pending JP2005059211A (en) | 2003-06-16 | 2003-07-11 | Gas barrier base material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2005059211A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006289821A (en) * | 2005-04-12 | 2006-10-26 | Fuji Photo Film Co Ltd | Gas barrier film, substrate film and organic electroluminescence device |
| JP2007015350A (en) * | 2005-07-11 | 2007-01-25 | Fujifilm Holdings Corp | Gas barrier film, substrate film and organic electroluminescence device |
| JP2010286285A (en) * | 2009-06-09 | 2010-12-24 | Toyo Seikan Kaisha Ltd | Unit and method for evaluating steam barrier properties |
| JP2020121425A (en) * | 2019-01-29 | 2020-08-13 | 倉敷紡績株式会社 | Barrier film |
-
2003
- 2003-07-11 JP JP2003196058A patent/JP2005059211A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006289821A (en) * | 2005-04-12 | 2006-10-26 | Fuji Photo Film Co Ltd | Gas barrier film, substrate film and organic electroluminescence device |
| US7815982B2 (en) | 2005-04-12 | 2010-10-19 | Fujifilm Corporation | Gas barrier film, substrate film, and organic electroluminescence device |
| JP2007015350A (en) * | 2005-07-11 | 2007-01-25 | Fujifilm Holdings Corp | Gas barrier film, substrate film and organic electroluminescence device |
| US7838092B2 (en) | 2005-07-11 | 2010-11-23 | Fujifilm Corporation | Gas barrier film, substrate film, and organic electroluminescence device |
| JP2010286285A (en) * | 2009-06-09 | 2010-12-24 | Toyo Seikan Kaisha Ltd | Unit and method for evaluating steam barrier properties |
| JP2020121425A (en) * | 2019-01-29 | 2020-08-13 | 倉敷紡績株式会社 | Barrier film |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI389367B (en) | Flexible substrate with film barrier layer | |
| CN1729310B (en) | Transparent Conductive Films for Flat Panel Displays | |
| Chen et al. | High-performance transparent barrier films of SiOx∕ SiNx stacks on flexible polymer substrates | |
| JP5879343B2 (en) | Flexible electronic element manufacturing method, flexible electronic element, and flexible substrate | |
| TWI550111B (en) | Self-passivation mechanism to stabilize the airtight film | |
| Kumar et al. | Low moisture permeation measurement through polymer substrates for organic light emitting devices | |
| JP5559542B2 (en) | Nanoparticle-encapsulated barrier stack | |
| JP6023402B2 (en) | Transparent conductive film and method for producing the same | |
| JP2008240150A (en) | Hermetic sealing using tin-containing inorganic material with low sintering temperature | |
| JP6181806B2 (en) | Transparent conductive film and method for producing the same | |
| JP3958235B2 (en) | Water vapor barrier evaluation cell and water vapor barrier evaluation method | |
| WO2017155902A1 (en) | Novel multilayer stacks including a stress relief layer, methods and compositions relating thereto | |
| JP5419868B2 (en) | Composite film and manufacturing method thereof | |
| JP2004009395A (en) | Transparent water vapor barrier film and its manufacturing process | |
| Gasonoo et al. | Parylene C-AlN multilayered thin-film passivation for organic light-emitting diode using a single deposition chamber | |
| Zhu et al. | Transparent flexible ultra‐low permeability encapsulation film: Fusible glass fired on heat‐resistant polyimide membrane | |
| JP2005059211A (en) | Gas barrier base material | |
| JP4289116B2 (en) | Gas barrier substrate, display device substrate and display device | |
| JP4106931B2 (en) | Transparent gas barrier thin film coating film | |
| JP2009226861A (en) | Gas barrier film | |
| JP2004009665A (en) | Optical film sheet with barrier film and display element using the same | |
| JP4617933B2 (en) | Film coated with glass with low softening point | |
| KR100941877B1 (en) | Passivation composition, sputtering target and passivation film using same, and method for manufacturing same | |
| JP2005036268A (en) | Sputtering target | |
| JP2009143759A (en) | Raw material powder of evaporation source material for ion plating, evaporation source material for ion plating and its manufacturing method and gas barrier sheet and its manufacturing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20060522 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20070322 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20080813 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080819 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20081216 |