JP5510348B2 - Evaluation method of water vapor barrier property - Google Patents
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本発明は、例えば、液晶ディスプレイ、有機ＥＬディスプレイ又は太陽電池等の機器、或いは食品、薬品等の包装材料等において、高い防湿性を付与するために用いられる水蒸気バリア膜の水蒸気バリア性を評価する方法に関する。 The present invention evaluates the water vapor barrier property of a water vapor barrier film used for imparting high moisture resistance, for example, in devices such as liquid crystal displays, organic EL displays or solar cells, or packaging materials such as foods and chemicals. Regarding the method.
液晶ディスプレイ、有機ＥＬディスプレイ又は太陽電池等の機器は、一般に湿気に弱く、吸湿によって急速にその特性を劣化させるため、高防湿性、即ち酸素や水蒸気等の透過又は侵入を防止するガスバリア性を有する部品を装備することが不可欠である。 Devices such as liquid crystal displays, organic EL displays, or solar cells are generally sensitive to moisture and rapidly deteriorate their characteristics due to moisture absorption. Therefore, they have high moisture resistance, that is, gas barrier properties that prevent permeation or penetration of oxygen, water vapor, and the like. It is essential to equip the parts.
例えば、太陽電池の例では、太陽電池モジュールの受光面とは反対側の裏面にバックシートが設けられている。このバックシートは、基材に、蒸着材等を用いて成膜された高防湿性を有する水蒸気バリア膜と、それらを保護する部材等から構成されたものが代表的なものである。また、上記太陽電池等の機器の他に、食品や薬品等の包装材料等でも高い水蒸気バリア性が求められており、プラスチックの表面に酸化珪素、酸化アルミ又はアルミ金属箔等を蒸着させて成膜した水蒸気バリア膜を備える包装材料等が一般的に広く知られている。 For example, in the example of a solar cell, the back sheet is provided on the back surface opposite to the light receiving surface of the solar cell module. This back sheet is typically composed of a water vapor barrier film having a high moisture-proof property formed on a base material using a vapor deposition material or the like, a member for protecting them, and the like. In addition to the above-mentioned devices such as solar cells, high water vapor barrier properties are also required for packaging materials such as foods and medicines. Silicon oxide, aluminum oxide, aluminum metal foil, etc. are deposited on the plastic surface. A packaging material provided with a filmed water vapor barrier film is generally widely known.
上記太陽電池のバックシート等が備える水蒸気バリア膜の水蒸気バリア性の評価は、これまで、カップ法（ＪＩＳ Ｚ ０２０８）やモコン法（ＪＩＳ Ｋ ７１２９）等によって評価されていたが、モコン法による水蒸気透過率の測定限界が０．０１／ｍ2・ｄａｙ程度であることから、有機ＥＬディスプレイ等に要求される高度な水蒸気バリア性の評価が困難であるという問題があった。このような問題を解消する評価方法として、水蒸気透過性を評価する材料から成る固体基板の片面側に、水分と反応して腐食する腐食性金属を形成した金属腐食試験片を湿度環境下に保管し、固体基板を透過した水蒸気によって腐食性金属の一部分が腐食した金属腐食試験片の画像を撮影し、撮影した画像の処理を行う画像処理手段を用いて水分と反応した金属の腐食状態を評価し、腐食領域の形状、分布及び/又は面積から固体基板の水蒸気透過性を評価する評価方法が開示されている（例えば、特許文献１参照。）。 The evaluation of the water vapor barrier property of the water vapor barrier film provided in the back sheet or the like of the solar cell has been evaluated by the cup method (JIS Z 0208), the mocon method (JIS K 7129), or the like. Since the measurement limit of the transmittance is about 0.01 / m 2 · day, there is a problem that it is difficult to evaluate the advanced water vapor barrier property required for an organic EL display or the like. As an evaluation method to eliminate such problems, a metal corrosion test piece in which a corrosive metal that reacts with moisture and corrodes is formed on one side of a solid substrate made of a material for evaluating water vapor permeability is stored in a humidity environment. Then, an image of a metal corrosion test piece in which part of the corrosive metal was corroded by water vapor that permeated through the solid substrate was evaluated, and the corrosion state of the metal that reacted with moisture was evaluated using an image processing means that processes the captured image. And the evaluation method which evaluates the water vapor permeability of a solid substrate from the shape, distribution, and / or area of a corrosion area is disclosed (for example, refer to patent documents 1).
しかしながら、上記モコン法等による評価方法では、高度な水蒸気バリア性の評価が困難であること以外にも、水蒸気透過率の実測には試験片を所定の温度、湿度環境下に長時間保持する必要があるため、非常に時間がかかるという問題がある。水蒸気透過率の実測に時間がかかると、製品の研究開発や品質検査、品質管理等に多大な時間を要することになり、その結果、製品の製造においても多大な時間と費用が発生するという問題が生じる。また、上記従来の特許文献１に示される評価方法では、金属腐食試験片を形成した後、測定と関係の無い大気中の水分から隔離するために、非腐食性金属やバリア性の高い透明酸化物で保護する、或いは硬化性樹脂とガラス基板で封止するなど、測定前の準備工程が煩雑であり、手間と時間がかかるといった問題があった。
However, in the evaluation method using the above-mentioned Mocon method and the like, it is necessary to hold the test piece for a long time in a predetermined temperature and humidity environment in order to measure the water vapor transmission rate, in addition to the difficulty of evaluating the high water vapor barrier property. There is a problem that it is very time consuming. If it takes time to actually measure the water vapor transmission rate, it will take a lot of time for product research and development, quality inspection, quality control, etc., and as a result, it takes a lot of time and money to produce the product. Occurs. Moreover, in the evaluation method shown in the above-mentioned
本発明の目的は、長時間を要する水蒸気透過率を実際に測定することなく、水蒸気バリア膜の水蒸気バリア性を迅速、かつ容易に評価することができる水蒸気バリア性の評価方法を提供することにある。 An object of the present invention is to provide a method for evaluating a water vapor barrier property capable of quickly and easily evaluating a water vapor barrier property of a water vapor barrier film without actually measuring a water vapor transmission rate that takes a long time. is there.
本発明の第１の観点は、第１酸化物（Ｘ）からなる蒸着材と第２酸化物（Ｙ）からなる蒸着材、或いは第１酸化物（Ｘ）及び第２酸化物（Ｙ）の双方を含む蒸着材を用い、真空成膜法により成膜した水蒸気バリア膜の水蒸気バリア性を評価する方法において、下記式（１）から算出されるＳ1の値を、温度４０℃、相対湿度９０％ＲＨの条件で１時間放置した後、温度４０℃、相対湿度９０％ＲＨの条件で測定される水蒸気バリア膜の水蒸気透過率Ｓ（ｇ／ｍ2・ｄａｙ）とみなして評価することを特徴とする。 According to a first aspect of the present invention, there is provided a vapor deposition material comprising the first oxide (X) and a second oxide (Y), or the first oxide (X) and the second oxide (Y). In a method for evaluating the water vapor barrier property of a water vapor barrier film formed by a vacuum film forming method using a vapor deposition material including both, the value of S 1 calculated from the following formula (1) is set to a temperature of 40 ° C. and a relative humidity. After being allowed to stand for 1 hour under the condition of 90% RH, the water vapor transmission rate S (g / m 2 · day) of the water vapor barrier film measured under the conditions of a temperature of 40 ° C. and a relative humidity of 90% RH is evaluated. Features.
ｌｏｇ10Ｓ1＝−０．０１５×（θ×ΔＢ）−０．２５ （１）
但し、式（１）中、θは成膜後、温度２５℃、相対湿度５０％ＲＨの条件で１日間保持した後の水蒸気バリア膜における水滴接触角を示し、ΔＢは第１酸化物（Ｘ）の塩基度Ｂｘと第２酸化物（Ｙ）の塩基度Ｂｙとの差の絶対値を示す。また、水蒸気バリア膜中の第１酸化物（Ｘ）の含有割合をｘモル、第２酸化物（Ｙ）の含有割合をｙモルとするとき、ｘ及びｙは０．０５≦ｘ／（ｘ＋ｙ）≦０．９５を満たす。
log 10 S 1 = −0.015 × (θ × ΔB) −0.25 (1)
However, in the formula (1), θ represents the water droplet contact angle in the water vapor barrier film after film formation and maintained for 1 day under the conditions of a temperature of 25 ° C. and a relative humidity of 50% RH, and ΔB represents the first oxide (X ) Shows the absolute value of the difference between the basicity Bx of the second oxide (Y) and the basicity By of the second oxide (Y). Further, when the content ratio of the first oxide (X) in the water vapor barrier film is x mol and the content ratio of the second oxide (Y) is y mol, x and y are 0.05 ≦ x / (x + y). ) ≦ 0.95 is satisfied.
本発明の第２の観点は、第１酸化物（Ｘ）からなる蒸着材と第２酸化物（Ｙ）からなる蒸着材、或いは第１酸化物（Ｘ）及び第２酸化物（Ｙ）の双方を含む蒸着材を用い、真空成膜法により成膜した水蒸気バリア膜の水蒸気バリア性を評価する方法において、下記式（２）及び式（３）の双方を満たすＳ2の範囲から、温度４０℃、相対湿度９０％ＲＨの条件で１時間放置した後、温度４０℃、相対湿度９０％ＲＨの条件で測定される水蒸気バリア膜の水蒸気透過率Ｓ（ｇ／ｍ2・ｄａｙ）を定めて評価することを特徴とする。
The second aspect of the present invention is that a vapor deposition material composed of the first oxide (X) and a vapor deposition material composed of the second oxide (Y), or the first oxide (X) and the second oxide (Y). In a method for evaluating the water vapor barrier property of a water vapor barrier film formed by a vacuum film formation method using a vapor deposition material containing both, the temperature is within the range of S 2 satisfying both of the following formulas (2) and (3). After standing for 1 hour under the conditions of 40 ° C. and
｛−０．０１５×（θ×ΔＢ）−０．２５｝−０．２５≦ｌｏｇ10Ｓ2 （２）
ｌｏｇ10Ｓ2≦｛−０．０１５×（θ×ΔＢ）−０．２５｝＋０．２５ （３）
但し、式（２）及び式（３）中、θは成膜後、温度２５℃、相対湿度５０％ＲＨの条件で１日間保持した後の水蒸気バリア膜における水滴接触角を示し、ΔＢは第１酸化物（Ｘ）の塩基度Ｂｘと第２酸化物（Ｙ）の塩基度Ｂｙとの差の絶対値を示す。また、水蒸気バリア膜中の第１酸化物（Ｘ）の含有割合をｘモル、第２酸化物（Ｙ）の含有割合をｙモルとするとき、ｘ及びｙは０．０５≦ｘ／（ｘ＋ｙ）≦０．９５を満たす。
{−0.015 × (θ × ΔB) −0.25} −0.25 ≦ log 10 S 2 (2)
log 10 S 2 ≦ {−0.015 × (θ × ΔB) −0.25} +0.25 (3)
However, in formula (2) and formula (3), θ represents the water droplet contact angle in the water vapor barrier film after film formation and after holding for 1 day at a temperature of 25 ° C. and a relative humidity of 50% RH. The absolute value of the difference between the basicity Bx of the first oxide (X) and the basicity By of the second oxide (Y) is shown. Further, when the content ratio of the first oxide (X) in the water vapor barrier film is x mol and the content ratio of the second oxide (Y) is y mol, x and y are 0.05 ≦ x / (x + y). ) ≦ 0.95 is satisfied.
本発明の第１の観点の評価方法では、第１酸化物（Ｘ）からなる蒸着材と第２酸化物（Ｙ）からなる蒸着材、或いは第１酸化物（Ｘ）及び第２酸化物（Ｙ）の双方を含む蒸着材を用い、真空成膜法により成膜した水蒸気バリア膜の水蒸気バリア性を評価する方法において、上記式（１）から算出されるＳ1の値を、温度４０℃、相対湿度９０％ＲＨの条件で１時間放置した後、温度４０℃、相対湿度９０％ＲＨの条件で測定される水蒸気バリア膜の水蒸気透過率Ｓ（ｇ／ｍ2・ｄａｙ）とみなして評価する。これにより、従来、多大な時間を要していた水蒸気透過率の実測をせずに、水蒸気バリア膜の水蒸気バリア性を迅速、かつ容易に評価することができる。 In the evaluation method of the 1st viewpoint of this invention, the vapor deposition material which consists of 1st oxide (X) and the 2nd oxide (Y), or 1st oxide (X) and 2nd oxide ( In the method for evaluating the water vapor barrier property of the water vapor barrier film formed by the vacuum film formation method using the vapor deposition material containing both of Y), the value of S 1 calculated from the above formula (1) is set to a temperature of 40 ° C. , After being allowed to stand for 1 hour at a relative humidity of 90% RH, the water vapor transmission rate S (g / m 2 · day) of the water vapor barrier film measured at a temperature of 40 ° C. and a relative humidity of 90% RH is evaluated. To do. This makes it possible to quickly and easily evaluate the water vapor barrier property of the water vapor barrier film without actually measuring the water vapor transmission rate, which has conventionally required a lot of time.
本発明の第２の観点の評価方法では、第１酸化物（Ｘ）からなる蒸着材と第２酸化物（Ｙ）からなる蒸着材、或いは第１酸化物（Ｘ）及び第２酸化物（Ｙ）の双方を含む蒸着材を用い、真空成膜法により成膜した水蒸気バリア膜の水蒸気バリア性を評価する方法において、式（２）及び式（３）の双方を満たすＳ2の範囲から、温度４０℃、相対湿度９０％ＲＨの条件で１時間放置した後、温度４０℃、相対湿度９０％ＲＨの条件で測定される水蒸気バリア膜の水蒸気透過率Ｓ（ｇ／ｍ2・ｄａｙ）を定めて評価する。このように、第２の観点の評価方法では、上記本発明の第１の観点の評価方法によって算出されたｌｏｇ10Ｓ1の値に、一定の範囲を付加して評価を行うことにより、式（１）から算出される値と実測値との間に比較的大きいな誤差が生じた場合でも、想定され得る誤差範囲を考慮した柔軟な評価を行うことができる。 In the evaluation method of the 2nd viewpoint of this invention, the vapor deposition material which consists of 1st oxide (X) and the 2nd oxide (Y), or 1st oxide (X) and 2nd oxide ( Y) In the method for evaluating the water vapor barrier property of the water vapor barrier film formed by the vacuum film formation method using the vapor deposition material containing both, from the range of S 2 satisfying both the formula (2) and the formula (3) The water vapor transmission rate S (g / m 2 · day) of the water vapor barrier film measured at a temperature of 40 ° C. and a relative humidity of 90% RH after being left for 1 hour at a temperature of 40 ° C. and a relative humidity of 90% RH Determine and evaluate. As described above, in the evaluation method according to the second aspect, the evaluation is performed by adding a certain range to the value of log 10 S 1 calculated by the evaluation method according to the first aspect of the present invention. Even when a relatively large error occurs between the value calculated from (1) and the actual measurement value, it is possible to perform a flexible evaluation in consideration of an error range that can be assumed.
次に本発明を実施するための形態を図面に基づいて説明する。
＜第１実施形態の評価方法＞
本発明第一実施形態の評価方法は、第１酸化物（Ｘ）からなる蒸着材と第２酸化物（Ｙ）からなる蒸着材、或いは第１酸化物（Ｘ）及び第２酸化物（Ｙ）の双方を含む蒸着材を用い、真空成膜法により成膜した水蒸気バリア膜の水蒸気バリア性を評価する新規な評価方法である。この評価方法で評価できる水蒸気バリア膜は、第１酸化物（Ｘ）からなる蒸着材と第２酸化物（Ｙ）からなる蒸着材の２つの蒸着材を、いわゆる共蒸着によって成膜した蒸着膜であっても良いし、第１酸化物（Ｘ）及び第２酸化物（Ｙ）の双方を含む１つの蒸着材を用いて、成膜した蒸着膜であってもよい。
Next, an embodiment for carrying out the present invention will be described with reference to the drawings.
<Evaluation Method of First Embodiment>
In the evaluation method of the first embodiment of the present invention, the vapor deposition material composed of the first oxide (X) and the vapor deposition material composed of the second oxide (Y), or the first oxide (X) and the second oxide (Y This is a novel evaluation method for evaluating the water vapor barrier property of a water vapor barrier film formed by a vacuum film formation method using a vapor deposition material containing both of the above. The vapor barrier film that can be evaluated by this evaluation method is a vapor deposition film in which two vapor deposition materials, ie, a vapor deposition material composed of a first oxide (X) and a vapor deposition material composed of a second oxide (Y), are formed by so-called co-deposition. Alternatively, a vapor deposition film formed using one vapor deposition material containing both the first oxide (X) and the second oxide (Y) may be used.
また、真空成膜法については特に限定されず、例えば、電子ビーム蒸着法、イオンプレーティング法、反応性プラズマ蒸着法、抵抗加熱法、誘導加熱法等のいずれの成膜方法によって成膜された蒸着膜であってもよい。 Further, the vacuum film forming method is not particularly limited. For example, the film is formed by any film forming method such as an electron beam vapor deposition method, an ion plating method, a reactive plasma vapor deposition method, a resistance heating method, an induction heating method, or the like. A vapor deposition film may be sufficient.
具体的には、下記式（１）から算出されるＳ1の値を、温度４０℃、相対湿度９０％ＲＨの条件で１時間放置した後、温度４０℃、相対湿度９０％ＲＨの条件で測定される水蒸気バリア膜の水蒸気透過率Ｓ（ｇ／ｍ2・ｄａｙ）とみなすことにより行う。 Specifically, the value of S 1 calculated from the following formula (1) is left for 1 hour at a temperature of 40 ° C. and a relative humidity of 90% RH, and then at a temperature of 40 ° C. and a relative humidity of 90% RH. This is performed by regarding the water vapor permeability S of the water vapor barrier film to be measured as S (g / m 2 · day).
ｌｏｇ10Ｓ1＝−０．０１５×（θ×ΔＢ）−０．２５ （１）
ここで、式（１）中、θは成膜後、温度２５℃、相対湿度５０％ＲＨの条件で１日間保持した後の水蒸気バリア膜における水滴接触角を示し、ΔＢは第１酸化物（Ｘ）の塩基度Ｂｘと第２酸化物（Ｙ）の塩基度Ｂｙとの差の絶対値を示す。また、水蒸気バリア膜中の第１酸化物（Ｘ）の含有割合をｘモル、第２酸化物（Ｙ）の含有割合をｙモルとするとき、ｘ及びｙは０．０５≦ｘ／（ｘ＋ｙ）≦０．９５を満たす。
log 10 S 1 = −0.015 × (θ × ΔB) −0.25 (1)
Here, in the formula (1), θ represents the water droplet contact angle in the water vapor barrier film after film formation and after holding for 1 day under the conditions of a temperature of 25 ° C. and a relative humidity of 50% RH, and ΔB represents the first oxide ( The absolute value of the difference between the basicity Bx of X) and the basicity By of the second oxide (Y) is shown. Further, when the content ratio of the first oxide (X) in the water vapor barrier film is x mol and the content ratio of the second oxide (Y) is y mol, x and y are 0.05 ≦ x / (x + y). ) ≦ 0.95 is satisfied.
水蒸気バリア膜の水蒸気バリア性には、本発明者らのこれまでの研究により、膜の内部構造（断面構造）が大きく影響するものと考えられている。例えば、図３に示す、基材１１上に形成される酸化物薄膜２２は、柱状晶の結晶がガスの浸透方向に対して平行に集合した構造になる。水蒸気等のガス分子は平行に集合した粒界の界面に沿って進むため、上記柱状晶の結晶が平行に集合した構造の薄膜２２ではバリア性が低いことになる。一方、図４に示すように、柱状晶の一部が崩れ、アモルファス状態に近い緻密な微細構造では、水蒸気等のガス分子は迷路状の中を長距離にわたり移動する必要があるため、このような構造の酸化物薄膜３２ではバリア性が向上することになる。
The water vapor barrier property of the water vapor barrier film is considered to be greatly influenced by the internal structure (cross-sectional structure) of the film by the present inventors' previous research. For example, the oxide
このような膜の内部構造には、成膜に用いられる蒸着材又はこれらに含まれる酸化物等の塩基度が大きく関係するものと考えられる。この「塩基度」は、森永健次らにより提案されたものであり、例えば彼の著書「K.Morinaga, H.Yoshida And H.Takebe:J.Am Cerm.Soc.,77,3113(1994)」の中で以下に示すような式を用いてガラス粉末の塩基度を規定している。この抜粋を以下に示す。 The internal structure of such a film is considered to be largely related to the basicity of the vapor deposition material used for film formation or the oxide contained therein. This `` basicity '' was proposed by Kenji Morinaga et al., For example, his book `` K. Morinaga, H. Yoshida And H. Takebe: J. Am Cerm. Soc., 77, 3113 (1994) ''. The basicity of the glass powder is defined using the following formula. This excerpt is shown below.
「酸化物ＭiＯのＭi−Ｏ間の結合力は陽イオン−酸素イオン間引力Ａiとして次式で与えられる。 "Coupling force between M i -O oxide M i O cation - given by the following equation as an oxygen ion attraction between A i.
Ａi＝Ｚi・Ｚ02-／（ｒi＋ｒ02-）2＝Ｚi・２／（ｒi＋１．４０）2
Ｚi：陽イオンの価数，酸素イオンは２
Ｒi：陽イオンのイオン半径（Å），酸素イオンは１．４０Å
このＡiの逆数Ｂi（１／Ａi）を単成分酸化物ＭiＯの酸素供与能力とする。
A i = Z i · Z 02− / (r i + r 02− ) 2 = Z i · 2 / (r i +1.40) 2
Z i : valence of cation, oxygen ion is 2
R i : cation radius (Å), oxygen ion is 1.40Å
The A i of the inverse B i a (1 / A i) a single-component oxide M i O oxygen donating ability.
Ｂi≡１／Ａi
このＢiをＢCaO＝１、ＢSiO2＝０と規格化すると、各単成分酸化物のＢi−指標が与えられる。」本発明において用いられる酸化物の塩基度は、ガラス粉末の塩基度の指標について、ガラスを酸化物と置き換えて解釈したものである。
B i ≡1 / A i
When the B i B CaO = 1, B SiO2 = to 0 and the normalized, B i of each single component oxides - index is given. The basicity of the oxide used in the present invention is an interpretation of the basicity index of glass powder by replacing glass with oxide.
また、水蒸気バリア膜の水蒸気バリア性には、膜の内部構造の他に、膜表面の撥水性等も大きく影響する。即ち、膜表面の撥水性が高ければ、膜内部に浸透する水蒸気の量を少なく抑えることができる。膜表面の撥水性を示す指標としては、固体表面に対する液体の吸着現象を表す尺度として一般的に用いられている水滴接触角が挙げられる。水滴接触角には、測定方法により、液適法、転落法、傾斜法等があり、本発明で規定する水滴接触角は、液滴法により、基板に成膜した膜にイオン交換水２μＬ滴下してから２秒後に測定されたものである。 In addition to the internal structure of the film, the water repellency of the film surface greatly affects the water vapor barrier property of the water vapor barrier film. That is, if the water repellency on the film surface is high, the amount of water vapor penetrating into the film can be reduced. As an index indicating the water repellency of the film surface, there is a water droplet contact angle generally used as a scale representing a liquid adsorption phenomenon on a solid surface. Depending on the measurement method, there are a liquid drop method, a drop method, a tilt method, etc., depending on the measurement method. The water drop contact angle specified in the present invention is obtained by dropping 2 μL of ion-exchanged water on the film formed on the substrate by the droplet method. It was measured 2 seconds after.
このような観点から、水蒸気バリア性の評価において、蒸着材に含まれる酸化物の塩基度と水滴接触角に着目し、本発明者らが研究を重ねたところ、実測された水蒸気バリア膜の水蒸気透過率、バリア膜の形成に用いられる蒸着材が含有する酸化物の塩基度、水蒸気バリア膜表面の水滴接触角の間には、ある一定の相関があることが判った。具体的には、複数の水蒸気バリア膜から測定された水蒸気透過率Ｓの実測値について、横軸をθ×ΔＢ、縦軸をｌｏｇ10Ｓとしてプロットしたときに、ｌｏｇ10Ｓの値とθ×ΔＢの値の間には上記式（１）に示すような傾きが負の比例関係があることが確認された。本発明において用いられる上記式（１）は、このときの複数の水蒸気バリア膜におけるｌｏｇ10Ｓの値とθ×ΔＢの値のデータから最小二乗法によって求められた直線である。 From this point of view, in the evaluation of the water vapor barrier property, the inventors of the present invention have repeatedly studied focusing on the basicity of the oxide contained in the vapor deposition material and the contact angle of the water droplets. It has been found that there is a certain correlation among the transmittance, the basicity of the oxide contained in the vapor deposition material used for forming the barrier film, and the water droplet contact angle on the surface of the water vapor barrier film. Specifically, the measured values of a plurality of water vapor barrier film as measured from the water vapor transmission rate S, the horizontal axis theta × .DELTA.B, the vertical axis when plotted as log 10 S, the log 10 S values and theta × It was confirmed that there is a negative proportional relationship between the values of ΔB as shown in the above equation (1). The equation (1) used in the present invention is a straight line obtained by the least square method from the log 10 S value and θ × ΔB value data in the plurality of water vapor barrier films at this time.
この直線を用いた具体的な評価手順は、次の通りである。先ず、酸化物（Ｘ）からなる蒸着材と、酸化物（Ｙ）からなる蒸着材を用いた共蒸着により、或いは酸化物（Ｘ）及び酸化物（Ｙ）の双方を含む蒸着材を用いて水蒸気バリア膜を成膜する。このとき、第１酸化物（Ｘ）の含有割合をｘモル、第２酸化物（Ｙ）の含有割合をｙモルとするときのｘ及びｙを０．０５≦ｘ／（ｘ＋ｙ）≦０．９５の範囲に限定する理由は、ｘ／（ｘ＋ｙ）が下限値未満又は上限値を越える水蒸気バリア膜については、本発明の方法では評価が困難であるからである。これは、ｘ／（ｘ＋ｙ）が下限値未満又は上限値を越えると、一方の酸化物の割合が少なくなりすぎて、他方の酸化物からなる単一組成の蒸着膜とほぼ同等になるからと推察される。なお、蒸着材に含まれる酸化物（Ｘ）又は酸化物（Ｙ）の塩基度は予め求めておく。次に、水蒸気バリア膜を、温度２５℃、相対湿度５０％ＲＨの条件で１日放置した後、水蒸気バリア膜の水滴接触角θを求める。水滴接触角を測定する際に、上記条件にて放置する理由は、成膜して間もない蒸着膜は、その表面状態が安定しておらず、水滴接触角の経時変化が著しいことから、測定される水滴接触角の値に大きなバラツキが生じるため、少なくとも１日間放置する必要があるからである。次に、酸化物（Ｘ）及び酸化物（Ｙ）の塩基度、及び上記測定された水滴接触角θを、式（１）に代入して、Ｓ1の値を求める。最後に、式（１）から求めたＳ1を水蒸気透過率Ｓの実測値、即ち温度４０℃、相対湿度９０％ＲＨの条件で１時間放置した後、温度４０℃、相対湿度９０％ＲＨの条件で、モコン法にて測定された水蒸気透過率とみなす。 A specific evaluation procedure using this straight line is as follows. First, by vapor deposition using a vapor deposition material made of oxide (X) and a vapor deposition material made of oxide (Y), or using a vapor deposition material containing both oxide (X) and oxide (Y). A water vapor barrier film is formed. At this time, when the content ratio of the first oxide (X) is x mol and the content ratio of the second oxide (Y) is y mol, x and y are 0.05 ≦ x / (x + y) ≦ 0. The reason for limiting to the range of 95 is that it is difficult to evaluate the water vapor barrier film in which x / (x + y) is less than the lower limit value or exceeds the upper limit value by the method of the present invention. This is because, when x / (x + y) is less than the lower limit value or exceeds the upper limit value, the ratio of one oxide is too small to be almost equivalent to a vapor deposition film of a single composition made of the other oxide. Inferred. Note that the basicity of the oxide (X) or oxide (Y) contained in the vapor deposition material is determined in advance. Next, the water vapor barrier film is allowed to stand for 1 day under conditions of a temperature of 25 ° C. and a relative humidity of 50% RH, and then a water droplet contact angle θ of the water vapor barrier film is obtained. The reason for leaving under the above conditions when measuring the water droplet contact angle is that the deposited film just after film formation is not stable in its surface state, and the water droplet contact angle changes with time, This is because a large variation occurs in the measured value of the water droplet contact angle, and it is necessary to leave it for at least one day. Next, the basicity of oxide (X) and oxide (Y) and the measured water droplet contact angle θ are substituted into equation (1) to determine the value of S 1 . Finally, S 1 obtained from the formula (1) is measured for the water vapor transmission rate S, that is, after standing for 1 hour under the conditions of a temperature of 40 ° C. and a relative humidity of 90% RH, then the temperature of 40 ° C. and the relative humidity of 90% RH It is regarded as the water vapor transmission rate measured by the Mocon method.
以上により、多大な時間を要する水蒸気透過率を実際に測定することなく、水蒸気バリア膜の水蒸気バリア性を容易に評価することができる。
＜第二実施形態の評価方法＞
本発明第二実施形態の評価方法は、上述した第一実施形態の評価方法と同様、第１酸化物（Ｘ）からなる蒸着材と第２酸化物（Ｙ）からなる蒸着材、或いは第１酸化物（Ｘ）及び第２酸化物（Ｙ）の双方を含む蒸着材を用い、真空成膜法により成膜した水蒸気バリア膜の水蒸気バリア性を評価する新規な評価方法である。この第二実施形態の評価方法では、下記式（２）及び式（３）の双方を満たすＳ2の範囲から、温度４０℃、相対湿度９０％ＲＨの条件で１時間放置した後、温度４０℃、相対湿度９０％ＲＨの条件で測定される水蒸気バリア膜の水蒸気透過率Ｓ（ｇ／ｍ2・ｄａｙ）を定めて評価する。
As described above, it is possible to easily evaluate the water vapor barrier property of the water vapor barrier film without actually measuring the water vapor transmission rate which takes a long time.
<Evaluation method of second embodiment>
The evaluation method of the second embodiment of the present invention is the same as the evaluation method of the first embodiment described above, the vapor deposition material composed of the first oxide (X) and the second oxide (Y), or the first This is a novel evaluation method for evaluating the water vapor barrier property of a water vapor barrier film formed by a vacuum film formation method using a vapor deposition material containing both oxide (X) and second oxide (Y). In the evaluation method of the second embodiment, after leaving for 1 hour at a temperature of 40 ° C. and a relative humidity of 90% RH from the range of S 2 satisfying both the following formulas (2) and (3), the temperature of 40 The water vapor transmission rate S (g / m 2 · day) of the water vapor barrier film measured under the conditions of ° C. and
｛−０．０１５×（θ×ΔＢ）−０．２５｝−０．２５≦ｌｏｇ10Ｓ2 （２）
ｌｏｇ10Ｓ2≦｛−０．０１５×（θ×ΔＢ）−０．２５｝＋０．２５ （３）
但し、式（２）及び式（３）中、θは成膜後、温度２５℃、相対湿度５０％ＲＨの条件で１日間保持した後の水蒸気バリア膜における水滴接触角を示し、ΔＢは第１酸化物（Ｘ）の塩基度Ｂｘと第２酸化物（Ｙ）の塩基度Ｂｙとの差の絶対値を示す。また、水蒸気バリア膜中の第１酸化物（Ｘ）の含有割合をｘモル、第２酸化物（Ｙ）の含有割合をｙモルとするとき、ｘ及びｙは０．０５≦ｘ／（ｘ＋ｙ）≦０．９５を満たす。
{−0.015 × (θ × ΔB) −0.25} −0.25 ≦ log 10 S 2 (2)
log 10 S 2 ≦ {−0.015 × (θ × ΔB) −0.25} +0.25 (3)
However, in formula (2) and formula (3), θ represents the water droplet contact angle in the water vapor barrier film after film formation and after holding for 1 day at a temperature of 25 ° C. and a relative humidity of 50% RH. The absolute value of the difference between the basicity Bx of the first oxide (X) and the basicity By of the second oxide (Y) is shown. Further, when the content ratio of the first oxide (X) in the water vapor barrier film is x mol and the content ratio of the second oxide (Y) is y mol, x and y are 0.05 ≦ x / (x + y). ) ≦ 0.95 is satisfied.
上記式（２）及び式（３）に、上記本発明第一実施形態の評価方法で使用する式（１）を代入すると、上記式（２）及び式（３）は、下記式（４）で表される。 When the formula (1) used in the evaluation method of the first embodiment of the present invention is substituted into the formula (2) and the formula (3), the formula (2) and the formula (3) are expressed by the following formula (4). It is represented by
ｌｏｇ10Ｓ1−０．２５≦ｌｏｇ10Ｓ2≦ｌｏｇ10Ｓ1＋０．２５ （４）
第二実施形態の評価方法では、上記式（４）に示されるように、上述した第一実施形態の評価方法に用いる上記式（１）から算出されるｌｏｇ10Ｓ1の値に、所定の範囲を設けて評価を行うものである。第一実施形態の評価方法では、上記式（１）から算出されるＳ1の値を、モコン法による水蒸気透過率そのものとみなすため、画一的かつ迅速な評価が可能である。一方、第１酸化物と第２酸化物が同じ場合、組成比が異なる膜でもΔＢは同一となるといった近似的要素を含むため、上記式（１）から算出されるＳ1の値と実測値との間には比較的大きな誤差が生じることがある。そのため、場合によっては想定される誤差の範囲まで把握しておく必要がある。そこで、この第二実施形態の評価方法は、上記式（１）からｌｏｇ10Ｓ1の値に一定の範囲を設けて評価を行うことにより、想定され得る実測値との誤差範囲までも考慮した柔軟な評価を可能にしたものである。なお、−０．２５〜＋０．２５という範囲は、上記式（１）を算出する際に用いた実測された水蒸気透過率Ｓのｌｏｇ10Ｓの値と、上記式（１）から算出されたｌｏｇ10Ｓ1の値の誤差の最大値を考慮して設定した範囲である。
log 10 S 1 −0.25 ≦ log 10 S 2 ≦ log 10 S 1 +0.25 (4)
In the evaluation method of the second embodiment, as shown in the above formula (4), the value of log 10 S 1 calculated from the above formula (1) used in the above-described evaluation method of the first embodiment is set to a predetermined value. A range is set for evaluation. In the evaluation method of the first embodiment, since the value of S 1 calculated from the above formula (1) is regarded as the water vapor transmission rate itself by the Mocon method, uniform and rapid evaluation is possible. On the other hand, when the first oxide and the second oxide are the same, since the ΔB is the same even in films having different composition ratios, the value of S 1 calculated from the above equation (1) and the actual measurement value are included. A relatively large error may occur between the two. Therefore, in some cases, it is necessary to grasp the range of the expected error. Therefore, the evaluation method of the second embodiment takes into consideration an error range from an actually measured value that can be assumed by setting a certain range to the value of log 10 S 1 from the above equation (1). This enables flexible evaluation. Note that the range of −0.25 to +0.25 was calculated from the log 10 S value of the actually measured water vapor transmission rate S used when calculating the above equation (1) and the above equation (1). This is a range set in consideration of the maximum error of the value of log 10 S 1 .
次に本発明の実施例を比較例とともに詳しく説明する。 Next, examples of the present invention will be described in detail together with comparative examples.
＜実施例１〜８＞
次の表１に示す条件にて、ガラス基板上に水蒸気バリア膜を成膜し試験片を得た。なお、水蒸気バリア膜の成膜は、反応性プラズマ蒸着法にて行い、実施例１〜７は第１酸化物（Ｘ）からなる蒸着材と第２酸化物（Ｙ）からなる蒸着材の２つの蒸着材を用いた共蒸着により、実施例８は第１酸化物（Ｘ）及び第２酸化物（Ｙ）の双方を含む１つの蒸着材を用いて行った。
<Examples 1-8>
Under the conditions shown in Table 1 below, a water vapor barrier film was formed on a glass substrate to obtain a test piece. The water vapor barrier film is formed by a reactive plasma vapor deposition method. Examples 1 to 7 are a vapor deposition material composed of a first oxide (X) and a vapor deposition material composed of a second oxide (Y). By co-evaporation using two vapor deposition materials, Example 8 was performed using one vapor deposition material containing both the first oxide (X) and the second oxide (Y).
次に、これらの試験片を、温度２５℃、相対湿度５０％ＲＨの条件で１日放置した後、水蒸気バリア膜の水滴接触角θを求めた。水滴接触角θは、ガラス基板に成膜した膜にイオン交換水２μＬ滴下してから２秒後に測定された液滴法による接触角である。上記酸化物（Ｘ）及び酸化物（Ｙ）の塩基度、及び上記測定された水滴接触角θを、下記式（１）に代入してＳ1の値（みなし値）をそれぞれ求めた。 Next, these test pieces were allowed to stand for 1 day under conditions of a temperature of 25 ° C. and a relative humidity of 50% RH, and then the water droplet contact angle θ of the water vapor barrier film was determined. The water droplet contact angle θ is a contact angle according to a droplet method measured 2 seconds after 2 μL of ion-exchanged water was dropped on a film formed on a glass substrate. The basicity of the oxide (X) and oxide (Y) and the measured water droplet contact angle θ were substituted into the following formula (1) to determine the value of S 1 (deemed value).
ｌｏｇ10Ｓ1＝−０．０１５×（θ×ΔＢ）−０．２５ （１）
この結果を次の表１に示す。また、式（１）から算出されたｌｏｇ10Ｓ1の値と、θ×ΔＢの値の関係を図２に示す。
log 10 S 1 = −0.015 × (θ × ΔB) −0.25 (1)
The results are shown in Table 1 below. FIG. 2 shows the relationship between the value of log 10 S 1 calculated from the equation (1) and the value of θ × ΔB.
＜比較試験及び評価＞
実施例１〜８と同じ条件で、水蒸気バリア膜を成膜した試験片をそれぞれ用意した。この試験片について、それぞれモコン法（ＪＩＳ Ｋ ７１２９）により、温度４０℃、相対湿度９０％ＲＨの条件で１時間放置した後、温度４０℃、相対湿度９０％ＲＨの条件にて水蒸気バリア膜の水蒸気透過率Ｓを測定し、これらを実測値とした。この結果を次の表１に示す。また、実測された水蒸気透過率Ｓのｌｏｇ10Ｓの値と、θ×ΔＢの値の関係を図２に示す。
<Comparison test and evaluation>
The test piece which formed the water vapor | steam barrier film | membrane on the same conditions as Examples 1-8 was each prepared. Each test piece was left for 1 hour under the conditions of a temperature of 40 ° C. and a relative humidity of 90% RH by the Mokon method (JIS K 7129), and then the water vapor barrier film was formed under the conditions of a temperature of 40 ° C. and a relative humidity of 90% RH. The water vapor transmission rate S was measured, and these were measured values. The results are shown in Table 1 below. FIG. 2 shows the relationship between the log 10 S value of the measured water vapor transmission rate S and the value of θ × ΔB.
更に、図２から明らかなように、実測された水蒸気透過率Ｓのｌｏｇ10Ｓの値は、いずれもｌｏｇ10Ｓ1−０．２５からｌｏｇ10Ｓ1＋０．２５の範囲内にあることが判る。このことから、例えば実施例６のように、式（１）から算出されたｌｏｇ10Ｓ1と、実測された水蒸気透過率Ｓのｌｏｇ10Ｓの値の間に比較的大きな誤差が生じた場合でも、ｌｏｇ10Ｓ1の値に上記範囲を付加して評価することで、想定される誤差範囲を把握しておくことができ、より柔軟な評価が行えることが確認された。 Further, as apparent from FIG. 2, the measured log 10 S values of the water vapor transmission rate S are all in the range of log 10 S 1 −0.25 to log 10 S 1 +0.25. I understand. From this, for example, as in Example 6, when a relatively large error occurs between the log 10 S 1 calculated from the expression (1) and the log 10 S value of the measured water vapor transmission rate S However, it was confirmed that by adding the above range to the value of log 10 S 1 and evaluating it, the assumed error range can be grasped and more flexible evaluation can be performed.
Claims (2)
下記式（１）から算出されるＳ1の値を、温度４０℃、相対湿度９０％ＲＨの条件で１時間放置した後、温度４０℃、相対湿度９０％ＲＨの条件で測定される前記水蒸気バリア膜の水蒸気透過率Ｓ（ｇ／ｍ2・ｄａｙ）とみなして評価することを特徴とする水蒸気バリア性の評価方法。
ｌｏｇ10Ｓ1＝−０．０１５×（θ×ΔＢ）−０．２５ （１）
但し、式（１）中、θは成膜後、温度２５℃、相対湿度５０％ＲＨの条件で１日間保持した後の前記水蒸気バリア膜における水滴接触角を示し、ΔＢは前記第１酸化物（Ｘ）の塩基度Ｂｘと前記第２酸化物（Ｙ）の塩基度Ｂｙとの差の絶対値を示す。また、前記水蒸気バリア膜中の第１酸化物（Ｘ）の含有割合をｘモル、前記第２酸化物（Ｙ）の含有割合をｙモルとするとき、ｘ及びｙは０．０５≦ｘ／（ｘ＋ｙ）≦０．９５を満たす。 Using a vapor deposition material made of the first oxide (X) and a vapor deposition material made of the second oxide (Y), or a vapor deposition material containing both the first oxide (X) and the second oxide (Y), a vacuum is used. In the method for evaluating the water vapor barrier property of the water vapor barrier film formed by the film forming method,
The value of S 1 calculated from the following formula (1) is allowed to stand for 1 hour under conditions of a temperature of 40 ° C. and a relative humidity of 90% RH, and then measured under the conditions of a temperature of 40 ° C. and a relative humidity of 90% RH. A method for evaluating water vapor barrier properties, characterized by evaluating water vapor permeability S (g / m 2 · day) of a barrier film.
log 10 S 1 = −0.015 × (θ × ΔB) −0.25 (1)
However, in the formula (1), θ represents a water droplet contact angle in the water vapor barrier film after film formation and maintained for 1 day under conditions of a temperature of 25 ° C. and a relative humidity of 50% RH, and ΔB represents the first oxide. The absolute value of the difference between the basicity Bx of (X) and the basicity By of the second oxide (Y) is shown. Further, when the content ratio of the first oxide (X) in the water vapor barrier film is x mol and the content ratio of the second oxide (Y) is y mol, x and y are 0.05 ≦ x / (X + y) ≦ 0.95 is satisfied.
下記式（２）及び式（３）の双方を満たすＳ2の範囲から、温度４０℃、相対湿度９０％ＲＨの条件で１時間放置した後、温度４０℃、相対湿度９０％ＲＨの条件で測定される前記水蒸気バリア膜の水蒸気透過率Ｓ（ｇ／ｍ2・ｄａｙ）を定めて評価することを特徴とする水蒸気バリア性の評価方法。
｛−０．０１５×（θ×ΔＢ）−０．２５｝−０．２５≦ｌｏｇ10Ｓ2 （２）
ｌｏｇ10Ｓ2≦｛−０．０１５×（θ×ΔＢ）−０．２５｝＋０．２５ （３）
但し、式（２）及び式（３）中、θは成膜後、温度２５℃、相対湿度５０％ＲＨの条件で１日間保持した後の前記水蒸気バリア膜における水滴接触角を示し、ΔＢは前記第１酸化物（Ｘ）の塩基度Ｂｘと前記第２酸化物（Ｙ）の塩基度Ｂｙとの差の絶対値を示す。また、前記水蒸気バリア膜中の第１酸化物（Ｘ）の含有割合をｘモル、前記第２酸化物（Ｙ）の含有割合をｙモルとするとき、ｘ及びｙは０．０５≦ｘ／（ｘ＋ｙ）≦０．９５を満たす。 Using a vapor deposition material made of the first oxide (X) and a vapor deposition material made of the second oxide (Y), or a vapor deposition material containing both the first oxide (X) and the second oxide (Y), a vacuum is used. In the method for evaluating the water vapor barrier property of the water vapor barrier film formed by the film forming method,
From the range of S 2 satisfying both of the following formulas (2) and (3), after standing for 1 hour at a temperature of 40 ° C. and a relative humidity of 90% RH, the temperature is 40 ° C. and a relative humidity of 90% RH. A method for evaluating a water vapor barrier property, characterized by determining and evaluating a water vapor permeability S (g / m 2 · day) of the water vapor barrier film to be measured.
{−0.015 × (θ × ΔB) −0.25} −0.25 ≦ log 10 S 2 (2)
log 10 S 2 ≦ {−0.015 × (θ × ΔB) −0.25} +0.25 (3)
However, in the formula (2) and the formula (3), θ represents a water droplet contact angle in the water vapor barrier film after film formation and held for 1 day under the conditions of a temperature of 25 ° C. and a relative humidity of 50% RH, and ΔB is The absolute value of the difference between the basicity Bx of the first oxide (X) and the basicity By of the second oxide (Y) is shown. Further, when the content ratio of the first oxide (X) in the water vapor barrier film is x mol and the content ratio of the second oxide (Y) is y mol, x and y are 0.05 ≦ x / (X + y) ≦ 0.95 is satisfied.
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