JP2012087390A - Vapor deposition material - Google Patents
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本発明は、蒸着用材料に関するものである。 The present invention relates to a vapor deposition material.
本発明の蒸着用材料を使用したガスバリア性蒸着フィルムは、例えば太陽電池のバックシート、食品や医薬品等の包装分野、あるいは非包装分野で酸素および水蒸気を遮断する必要がある部材の分野に広く用いることができる。 The gas barrier vapor-deposited film using the vapor deposition material of the present invention is widely used, for example, in the field of components that need to block oxygen and water vapor in the back sheet of solar cells, the packaging field of foods and pharmaceuticals, or the non-packaging field. be able to.
ハードディスクや半導体モジュールなどの精密電子部品類、あるいは、食品や医薬品類の包装に用いられる包装材料は、内容物を保護することが必要である。特に、食品包装においては蛋白質や油脂などの酸化や変質を抑制し、味や鮮度を保持することが必要である。 It is necessary to protect the contents of precision electronic parts such as hard disks and semiconductor modules, or packaging materials used for packaging foods and pharmaceuticals. Particularly in food packaging, it is necessary to suppress the oxidation and alteration of proteins, fats and oils, and to maintain the taste and freshness.
また無菌状態での取り扱いが必要とされる医薬品類においては有効成分の変質を抑制し、効能を維持すること、さらに、精密電子部品類においては金属部分の腐食、絶縁不良などを防止するために、包装材料を透過する酸素や水蒸気、その他内容物を変質させる気体を遮断するガスバリア性を備える包装体が求められている。 In order to prevent the active ingredient from being altered and maintain its efficacy in pharmaceuticals that require handling under aseptic conditions, and to prevent corrosion of metal parts and poor insulation in precision electronic parts. There is a need for a package having a gas barrier property that blocks oxygen, water vapor, and other gases that alter the contents of the packaging material.
そのため、従来から温度、湿度などに影響されないアルミニウムなどの金属箔やアルミニウム蒸着フィルムあるいは、ポリビニルアルコール（ＰＶＡ）、エチレン‐ビニルアルコール共重合体（ＥＶＯＨ）、ポリ塩化ビニリデン（ＰＶＤＣ）、ポリアクリロニトリル（ＰＡＮ）などの樹脂フィルムやこれらの樹脂をラミネートまたはコーティングしたプラスチックフィルムなどが好んで用いられてきた。 Therefore, metal foils such as aluminum and aluminum deposited films that are not affected by temperature, humidity, etc., polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (EVOH), polyvinylidene chloride (PVDC), polyacrylonitrile (PAN). ) And plastic films laminated or coated with these resins have been used favorably.
ところが、アルミニウムなどの金属箔やアルミニウム蒸着フィルムを用いた包装材料は、ガスバリア性には優れるが、不透明であるため、包装材料を透過して内容物を識別することが難しいだけではなく、使用後の廃棄の際に不燃物として処理しなければならいない点や金属探知機による異物検査や、電子レンジでの加熱処理が出来ない点などの欠点を有していた。 However, packaging materials using metal foils such as aluminum and aluminum vapor-deposited films are excellent in gas barrier properties, but are opaque, so it is difficult not only to identify the contents through the packaging material, but also after use. However, it has the disadvantages that it must be treated as an incombustible material at the time of disposal, a foreign matter inspection using a metal detector, and a heat treatment in a microwave oven cannot be performed.
また、ガスバリア性樹脂フィルムやガスバリア性樹脂をコーティングしたフィルムは、温度依存性が大きく、高いガスバリア性を維持できない。さらに、使用後ＰＶＤＣやＰＡＮなどは廃棄・焼却の際に有害物質が発生する原因となる可能性などの問題があった。 In addition, a gas barrier resin film or a film coated with a gas barrier resin is highly temperature dependent and cannot maintain high gas barrier properties. Furthermore, after use, PVDC, PAN, and the like have problems such as the possibility of causing harmful substances during disposal and incineration.
そこで、これらの欠点を克服した包装用材料として、最近では酸化マグネシウム、酸化カルシウム、酸化アルミニウム、酸化珪素などの無機酸化物を透明な基材フィルム上に蒸着したガスバリア性フィルムが上市されている。 Therefore, as a packaging material that overcomes these drawbacks, a gas barrier film in which an inorganic oxide such as magnesium oxide, calcium oxide, aluminum oxide, or silicon oxide is vapor-deposited on a transparent base film has recently been put on the market.
これらのガスバリア性蒸着フィルムは透明性および酸素、水蒸気などのガス遮断性を有していることが知られ、金属箔などでは得ることの出来ない透明性、ガスバリア性の両方を有する包装材料として好適とされており、酸化珪素ＳｉＯｘを蒸着したフィルムでは食品包装用フィルムとして用いられている。また、酸化珪素ＳｉＯｘを蒸着用材料とした加熱方式による蒸着は非常に成膜速度が速く、生産性が高い。 These gas barrier vapor-deposited films are known to have transparency and gas barrier properties such as oxygen and water vapor, and are suitable as packaging materials having both transparency and gas barrier properties that cannot be obtained with metal foil or the like. In the film deposited with silicon oxide SiOx, it is used as a food packaging film. In addition, vapor deposition by a heating method using silicon oxide SiOx as a vapor deposition material has a very high film formation rate and high productivity.
しかし、ここで用いられている蒸着用材料の酸化珪素のＳｉＯｘ（０＜ｘ＜２）は、金属珪素と二酸化珪素を原料として真空蒸着により製造されるため、次に示すような欠点を有している。 However, the silicon oxide SiOx (0 <x <2), which is a deposition material used here, is manufactured by vacuum deposition using metal silicon and silicon dioxide as raw materials, and thus has the following drawbacks. ing.
真空蒸着法により製造する蒸着用材料の酸化珪素ＳｉＯｘ（０＜ｘ＜２）は大量生産に適した製造方法ではないため、材料費が高く、製造コストが高くなるという問題がある。また、この蒸着用材料の酸化珪素ＳｉＯｘ（０＜ｘ＜２）は真密度に近い密度を有し、非常に緻密な構造になっている。 Since silicon oxide SiOx (0 <x <2), which is a material for vapor deposition produced by vacuum vapor deposition, is not a production method suitable for mass production, there is a problem that the material cost is high and the production cost is high. Further, the silicon oxide SiOx (0 <x <2) of this vapor deposition material has a density close to the true density and has a very dense structure.
そのため、この蒸着用材料を蒸発させてバリアフィルムを製造した場合には、蒸着の際の加熱による熱衝撃や内部から発生するガスの圧力により、気化していない蒸着用材料が高温の粒子として飛散するスプラッシュという現象が発生するという問題がある。 Therefore, when a barrier film is produced by evaporating this deposition material, unvaporized deposition material is scattered as high-temperature particles due to thermal shock caused by heating during vapor deposition or the pressure of gas generated from the inside. There is a problem that a phenomenon called splash occurs.
高温の粒子が高分子フィルム上に到達した際には、ピンホールや異物が生じ、バリア性の低下および外観不良となる。さらに、上記記載の加熱方式、特に電子銃による加熱は、より大きい熱衝撃を蒸着用材料が受けることで上記のスプラッシュと異物の発生がより顕著に現れる。 When high-temperature particles reach the polymer film, pinholes and foreign matters are generated, resulting in a decrease in barrier properties and poor appearance. Further, in the heating method described above, particularly heating by an electron gun, the above-described splash and foreign matter are more noticeably generated when the deposition material receives a larger thermal shock.
これに対して金属珪素と二酸化珪素の混合蒸着用材料は、比較的安価であるが、加熱時に一酸化珪素よりも蒸気圧が高いために蒸発しにくく、さらに溶融型の蒸着用材料であるため、より大きい熱衝撃が必要となり、蒸着用材料が飛散してスプラッシュが発生しやすい。また、二酸化珪素の分解による酸素ガスの発生で成膜室内の圧力が上昇し、蒸着速度の低下、つまり生産性の低下が起こり、また蒸着膜密度の低下による蒸着膜のバリア性の低下を引き起こす問題もある。
公知技術としては、例えば下記の特許文献１〜２が挙げられる。
On the other hand, the mixed vapor deposition material of metal silicon and silicon dioxide is relatively inexpensive, but it is difficult to evaporate because it has a higher vapor pressure than silicon monoxide during heating, and it is a melt type vapor deposition material. Therefore, a larger thermal shock is required, and the vapor deposition material is scattered and splash is likely to occur. In addition, the generation of oxygen gas due to the decomposition of silicon dioxide increases the pressure in the film formation chamber, resulting in a decrease in deposition rate, that is, a decrease in productivity, and a decrease in barrier properties of the deposited film due to a decrease in deposited film density. There is also a problem.
Examples of known techniques include the following Patent Documents 1 and 2.
本発明は、以上の従来技術の問題を解決しようとするものであり、スプラッシュ現象の発生を抑制し、高いガスバリア性を付与できる蒸着用材料を提供することを目的とする。 The present invention is intended to solve the above-described problems of the prior art, and an object of the present invention is to provide a vapor deposition material that can suppress the occurrence of a splash phenomenon and can provide high gas barrier properties.
本発明は係る課題に鑑みなされたものであり、請求項１に記載の発明は、金属珪素と、二酸化珪素と、酸化マグネシウム粉末とを含有してなる加熱方式の蒸着用材料であって、珪素とマグネシウムの合計の原子数と、酸素の原子数の比（Ｏ／（Ｓｉ＋Ｍｇ））が１．０〜１．８であり、マグネシウムと珪素の原子数の比（Ｍｇ／Ｓｉ）が０．０２〜０．５０であることを特徴とする蒸着用材料である。 The present invention has been made in view of the above problems, and the invention according to claim 1 is a heating type vapor deposition material containing metallic silicon, silicon dioxide, and magnesium oxide powder, And the ratio of the total number of atoms of magnesium and the number of oxygen atoms (O / (Si + Mg)) is 1.0 to 1.8, and the ratio of the number of magnesium and silicon atoms (Mg / Si) is 0.02. It is -0.50, It is a material for vapor deposition characterized by the above-mentioned.
請求項２に記載の発明は、嵩密度が０．９〜１．５ｇ／ｃｍ３の範囲であることを特徴とする請求項１に記載の蒸着用材料である。 Invention of Claim 2 is a vapor deposition material of Claim 1 whose bulk density is the range of 0.9-1.5 g / cm < 3 >.
請求項３に記載の発明は、前記金属珪素と前記二酸化珪素の合計に対し、前記金属珪素粉末の割合が５〜３０重量％であり、前記酸化マグネシウムと前記金属珪素における珪素のｍｏｌ比（ＭｇＯ／Ｓｉ）が０．１〜２．０であることを特徴とする請求項１に記載の蒸着用材料である。 In the invention according to claim 3, the ratio of the metal silicon powder to the total of the metal silicon and the silicon dioxide is 5 to 30% by weight, and the molar ratio of the silicon in the magnesium oxide and the metal silicon (MgO 2. The deposition material according to claim 1, wherein / Si) is 0.1 to 2.0.
請求項４に記載の発明は、前記酸化マグネシウム粉末の純度が９９．９％以上であることを特徴とする請求項１に記載の蒸着用材料である。 The invention according to claim 4 is the vapor deposition material according to claim 1, wherein the magnesium oxide powder has a purity of 99.9% or more.
請求項５に記載の発明は、カルシウムの濃度が１００ｐｐｍ以下であり、かつ酸化マグネシウム粉末に含まれるカルシウムの濃度が１，０００ｐｐｍ以下であることを特徴とする請求項４に記載の蒸着用材料である。 The invention according to claim 5 is the vapor deposition material according to claim 4, wherein the concentration of calcium is 100 ppm or less and the concentration of calcium contained in the magnesium oxide powder is 1,000 ppm or less. is there.
本発明の蒸着用材料によれば、生産性向上のために高い出力での電子ビーム加熱蒸着法を利用した場合でもスプラッシュ現象を抑制でき、高いガスバリア性の蒸着フィルムを得ることができる。 According to the vapor deposition material of the present invention, a splash phenomenon can be suppressed even when an electron beam heating vapor deposition method with a high output is used to improve productivity, and a vapor deposition film having a high gas barrier property can be obtained.
以下に、本発明の実施の形態について説明する。
本発明で蒸着用材料として使用される金属珪素と、二酸化珪素と、酸化マグネシウム粉末とを含有してなる加熱方式の蒸着用材料は、珪素とマグネシウムの合計の原子数と酸素の原子数の比（Ｏ／（Ｓｉ＋Ｍｇ））、マグネシウムと珪素の原子数の比（Ｍｇ／Ｓｉ）、および、好適には嵩密度を管理することで、電子ビームによる熱衝撃に対して破壊されにくく、即ち、耐熱衝撃性が向上し、スプラッシュ現象を抑制するものである。
Embodiments of the present invention will be described below.
In the present invention, the heating type vapor deposition material containing metallic silicon, silicon dioxide, and magnesium oxide powder used as the vapor deposition material is a ratio of the total number of atoms of silicon and magnesium to the number of oxygen atoms. (O / (Si + Mg)), the ratio of the number of atoms of magnesium and silicon (Mg / Si), and preferably by controlling the bulk density, it is difficult to be destroyed by thermal shock caused by an electron beam. The impact property is improved and the splash phenomenon is suppressed.
そして、電子ビーム加熱による蒸着の際には、好適には嵩密度を管理することで、緻密構造にならないようにして熱伝導性を低くすることと、低い熱伝導性を持つ二酸化珪素を混合したことにより、電子ビーム加熱による急激な温度上昇による突沸の発生を抑制し、スプラッシュ現象を低減させたものである。 And in the case of vapor deposition by electron beam heating, preferably by controlling the bulk density, the thermal conductivity is lowered so as not to become a dense structure, and silicon dioxide having a low thermal conductivity is mixed. As a result, the occurrence of bumping due to a rapid temperature rise due to electron beam heating is suppressed, and the splash phenomenon is reduced.
また、二酸化珪素が加熱されると酸素ガスが脱離し、加熱された金属珪素も二酸化珪素から発生した酸素ガスが近傍にあるため、突沸することなく反応しＳｉＯｘ蒸気となる。また、酸化マグネシウムも蒸発しＭｇＯｙ蒸気となることで、高分子基材フィルム上にＳｉＯｘ・ＭｇＯｙ膜を形成できる。また、蒸着材料の表層には溶融した二酸化珪素が残ることでスプラッシュを抑制し、高いバリア性を持つ蒸着フィルムを形成できると考えられる。 Also, when silicon dioxide is heated, oxygen gas is desorbed, and the heated metal silicon reacts without bumping because it is in the vicinity of oxygen gas generated from silicon dioxide, and becomes SiOx vapor. Further, the magnesium oxide also evaporates into MgOy vapor, so that a SiOx / MgOy film can be formed on the polymer substrate film. Moreover, it is thought that the melted silicon dioxide remains on the surface layer of the vapor deposition material, thereby suppressing splash and forming a vapor deposition film having high barrier properties.
本発明の金属珪素と、二酸化珪素と、酸化マグネシウム粉末とを含有してなる加熱方式の蒸着用材料に関して、その珪素とマグネシウムの合計の原子数と、酸素の原子数の比（Ｏ／（Ｓｉ＋Ｍｇ））は１．０〜１．８が望ましい。前記のＯ／（Ｓｉ＋Ｍｇ）が１．０未満では、材料に含まれる二酸化珪素が少ないため、材料表層の溶融部分が少なく、スプラッシュが発生し易く、Ｏ／（Ｓｉ＋Ｍｇ）が１．８を超えると、酸素ガスの発生が多くなるため、成膜室内の圧力が上昇し、蒸着速度の低下、つまり生産性の低下が起こり、また蒸着膜密度の低下により蒸着膜のバリア性が低下する。 Regarding the heating-type vapor deposition material containing metal silicon, silicon dioxide and magnesium oxide powder of the present invention, the ratio of the total number of atoms of silicon and magnesium to the number of oxygen atoms (O / (Si + Mg )) Is preferably 1.0 to 1.8. When the above O / (Si + Mg) is less than 1.0, since the silicon dioxide contained in the material is small, the melted portion of the material surface layer is small, splash is likely to occur, and when O / (Si + Mg) exceeds 1.8. Since the generation of oxygen gas increases, the pressure in the deposition chamber increases, the deposition rate decreases, that is, the productivity decreases, and the deposited film density decreases, and the barrier property of the deposited film decreases.
また、金属珪素と、二酸化珪素と、酸化マグネシウム粉末とを含有してなる加熱方式の蒸着用材料に関して、そのマグネシウムと珪素の原子数の比（Ｍｇ／Ｓｉ）は０．０２〜０．５０が望ましい。前記のＭｇ／Ｓｉが０．０２未満では、マグネシウム成分を添加することによるバリア性向上効果が得られず、Ｍｇ／Ｓｉが０．５０を超えると、蒸着したフィルムに含まれるマグネシウムの量が多くなるため、フィルムの耐水性が低下する。 In addition, regarding a heating-type vapor deposition material containing metal silicon, silicon dioxide, and magnesium oxide powder, the ratio of the number of atoms of magnesium and silicon (Mg / Si) is 0.02 to 0.50. desirable. If the Mg / Si is less than 0.02, the effect of improving the barrier property by adding the magnesium component cannot be obtained. If Mg / Si exceeds 0.50, the amount of magnesium contained in the deposited film is large. Therefore, the water resistance of the film is lowered.
また、蒸着用材料の嵩密度は０．９〜１．５ｇ／ｃｍ３が好ましい。混合蒸着用材料の嵩密度が０．９ｇ／ｃｍ３未満では、蒸着用材料の割れや飛散が発生し易く、嵩密度が１．５ｇ／ｃｍ３を超えると、材料の蒸発に必要なエネルギーがより必要となるため、蒸発レートが低くなり、蒸着速度の低下、つまり生産性が低下する。 Further, the bulk density of the vapor deposition material is preferably 0.9 to 1.5 g / cm 3 . If the bulk density of the mixed vapor deposition material is less than 0.9 g / cm 3 , the vapor deposition material is likely to be cracked or scattered. If the bulk density exceeds 1.5 g / cm 3 , the energy required for evaporation of the material is increased. Since it is more necessary, the evaporation rate is lowered, and the deposition rate is lowered, that is, the productivity is lowered.
さらに、蒸着用材料はそれぞれ同程度の粒径を用いると混ざりやすく、１μｍ〜１００μｍの粉末を用いることで蒸着用材料の昇温プロセスが簡易になる。これは、金属珪素が蒸着用材料に均一に混合されることで、材料が温まり易く電子ビームのデフォーカスが起こりにくいためと考えられる。 Further, the vapor deposition materials are easily mixed when using the same particle size, and the temperature raising process of the vapor deposition material is simplified by using a powder of 1 μm to 100 μm. This is presumably because the metal silicon is uniformly mixed with the vapor deposition material, so that the material is easily heated and the electron beam is not easily defocused.
また本発明の蒸着用材料は、前記金属珪素と前記二酸化珪素の合計に対し、前記金属珪素粉末の割合が５〜３０重量％であることが好ましい。酸化マグネシウムと金属珪素が共存することで、詳細は不明であるが、 酸化マグネシウムが金属珪素によって還元（金属珪素は酸化）され、安定した蒸発が得られかつ蒸発速度の低下など不具合なく好適であった。一般に珪素化合物系材料の蒸発温度に比べ、酸化マグネシウムは蒸発温度が高いが、共存させることで、混合材料において安定した蒸発が得られたと考えられる。特に、前記酸化マグネシウムと前記金属珪素における珪素のｍｏｌ比（ＭｇＯ／Ｓｉ）が０．１〜２．０の場合、さらに望ましくは０．３〜１．５において安定した蒸発が得られ好適であった。 Moreover, it is preferable that the ratio of the said metal silicon powder is 5-30 weight% with respect to the sum total of the said metal silicon and the said silicon dioxide in the vapor deposition material of this invention. Although the details are unknown due to the coexistence of magnesium oxide and metal silicon, magnesium oxide is reduced by metal silicon (metal silicon is oxidized), stable evaporation is obtained, and it is suitable without problems such as a decrease in evaporation rate. It was. In general, magnesium oxide has a higher evaporation temperature than the evaporation temperature of a silicon compound-based material, but it is considered that stable evaporation was obtained in the mixed material by coexistence. In particular, when the molar ratio (MgO / Si) of the silicon in the magnesium oxide and the metal silicon is 0.1 to 2.0, it is more preferable that stable evaporation is obtained at 0.3 to 1.5. It was.
本発明で使用する蒸着用材料の、酸化マグネシウムの純度は９５．０％以上が望ましく、さらには９９．９％以上がより望ましい。酸化マグネシウムの純度が９５．０％以下では、微量不純物による蒸着の妨げがおこり、バリア性が低下する。 The purity of magnesium oxide of the vapor deposition material used in the present invention is desirably 95.0% or more, and more desirably 99.9% or more. When the purity of magnesium oxide is 95.0% or less, vapor deposition is hindered by a trace amount of impurities, and the barrier property is lowered.
本発明で使用する蒸着用材料の、カルシウム濃度は１００ｐｐｍ以下が望ましく、かつ酸化マグネシウム粉末に含まれるカルシウムの濃度は１，０００ｐｐｍ以下が望ましい。蒸着用材料のカルシウム濃度および／または酸化マグネシウム粉末に含まれるカルシウムの濃度が上記範囲を満たさないと、カルシウム成分による蒸着の妨げがおこり、バリア性が低下し、さらにスプラッシュが発生しやすくなる。 The calcium concentration of the vapor deposition material used in the present invention is desirably 100 ppm or less, and the concentration of calcium contained in the magnesium oxide powder is desirably 1,000 ppm or less. If the calcium concentration of the material for vapor deposition and / or the concentration of calcium contained in the magnesium oxide powder does not satisfy the above range, the vapor deposition is hindered by the calcium component, the barrier property is lowered, and splash is more likely to occur.
本発明の蒸着用材料は、珪素とマグネシウムの合計の原子数と酸素の原子数の比（Ｏ／（Ｓｉ＋Ｍｇ））、マグネシウムと珪素の原子数の比（Ｍｇ／Ｓｉ）、また好適には嵩密度を管理すること、酸化マグネシウムの純度を高純度にすること、また材料中のカルシウム濃度を抑制することで、従来の蒸着用材料に比べスプラッシュ現象を生じさせることなく、高いバリア性を持つ蒸着フィルムを形成できる蒸着用材料を得ることができる。 The vapor deposition material of the present invention comprises a ratio of the total number of atoms of silicon and magnesium to the number of atoms of oxygen (O / (Si + Mg)), a ratio of the number of atoms of magnesium and silicon (Mg / Si), and preferably a bulk. Evaporation with high barrier properties without causing a splash phenomenon compared to conventional deposition materials by controlling the density, increasing the purity of magnesium oxide, and suppressing the calcium concentration in the material An evaporation material capable of forming a film can be obtained.
以下に、本発明の実施例を具体的に説明する。 Examples of the present invention will be specifically described below.
＜実施例１＞
金属珪素には５０μｍ以下の径を有する粉末が９５％以上のものを使用し、二酸化珪素には結晶構造を９５％含み、５０μｍ以下の径を有する粉末が９５％以上のものを使用し、酸化マグネシウムには純度９９．９％かつカルシウム濃度が２０ｐｐｍのものを使用した。珪素とマグネシウムの合計の原子数と酸素の原子数の比（Ｏ／（Ｓｉ＋Ｍｇ））が１．４となるようにし、マグネシウと珪素の原子数の比（Ｍｇ／Ｓｉ）が０．１３となるように混合した金属珪素と二酸化珪素と酸化マグネシウムからなる蒸着用材料を作製した。この蒸着用材料を坩堝に投入し、嵩密度が１．０ｇ／ｃｍ３となるようにプレス成型した。
<Example 1>
For metal silicon, a powder having a diameter of 50 μm or less is 95% or more, and for silicon dioxide, a crystal structure containing 95% is used, and a powder having a diameter of 50 μm or less is 95% or more. Magnesium having a purity of 99.9% and a calcium concentration of 20 ppm was used. The ratio of the total number of atoms of silicon and magnesium to the number of oxygen atoms (O / (Si + Mg)) is 1.4, and the ratio of the number of atoms of magnesium and silicon (Mg / Si) is 0.13. A vapor deposition material composed of metallic silicon, silicon dioxide, and magnesium oxide mixed as described above was produced. This vapor deposition material was put into a crucible and press-molded so that the bulk density was 1.0 g / cm 3 .
電子ビーム加熱方式の真空蒸着装置で、電子銃から放出する電子ビームを蒸着用材料に照射し蒸発させ、高分子フィルム基材上に成膜した。 In an electron beam heating type vacuum deposition apparatus, the deposition material was irradiated with an electron beam emitted from an electron gun and evaporated to form a film on a polymer film substrate.
＜実施例２＞
実施例１で作製した蒸着用材料と同様に、珪素とマグネシウムの合計の原子数と酸素の原子数の比（Ｏ／（Ｓｉ＋Ｍｇ））が１．２となるようにし、マグネシウと珪素の原子数の比（Ｍｇ／Ｓｉ）が０．１２となるように混合した金属珪素と二酸化珪素と酸化マグネシウムからなる蒸着用材料を作製した。この混合蒸着用材料を坩堝に投入し、嵩密度が１．０ｇ／ｃｍ３となるようにプレス成型した。
<Example 2>
Similar to the vapor deposition material produced in Example 1, the ratio of the total number of atoms of silicon and magnesium to the number of atoms of oxygen (O / (Si + Mg)) is 1.2, and the number of atoms of magnesium and silicon. An evaporation material made of metallic silicon, silicon dioxide, and magnesium oxide mixed so that the ratio (Mg / Si) was 0.12 was prepared. This mixed vapor deposition material was put into a crucible and press-molded so that the bulk density was 1.0 g / cm 3 .
以下に本発明の比較例について説明する。 Hereinafter, comparative examples of the present invention will be described.
＜比較例１＞
金属珪素には５０μｍ以下の径を有する粉末が９５％以上のものを使用し、二酸化珪素には結晶構造を９５％含み、５０μｍ以下の径を有する粉末が９５％以上のものを使用した。珪素の原子数と酸素の原子数の比（Ｏ／Ｓｉ）が１．５となるように混合した金属珪素と二酸化珪素からなる蒸着用材料を作製した。この蒸着用材料を坩堝に投入し、嵩密度が１．０ｇ／ｃｍ３となるようにプレス成型した。
<Comparative Example 1>
The metal silicon used was a powder having a diameter of 50 μm or less of 95% or more, and the silicon dioxide containing a crystal structure containing 95% and a powder having a diameter of 50 μm or less was 95% or more. An evaporation material made of metal silicon and silicon dioxide mixed so that the ratio of the number of silicon atoms to the number of oxygen atoms (O / Si) was 1.5 was prepared. This vapor deposition material was put into a crucible and press-molded so that the bulk density was 1.0 g / cm 3 .
＜比較例２＞
実施例１で作製した混合蒸着用材料と同様に、珪素とマグネシウムの合計の原子数と酸素の原子数の比（Ｏ／（Ｓｉ＋Ｍｇ））が１．３となるようにし、マグネシウと珪素の原子数の比（Ｍｇ／Ｓｉ）が０．６５となるように混合した金属珪素と二酸化珪素と酸化マグネシウムからなる混合蒸着用材料を作製した。この混合蒸着用材料を坩堝に投入し、嵩密度が１．０ｇ／ｃｍ３となるようにプレス成型した。
<Comparative example 2>
Similarly to the mixed vapor deposition material produced in Example 1, the ratio of the total number of atoms of silicon and magnesium to the number of oxygen atoms (O / (Si + Mg)) is 1.3, so that the atoms of magnesium and silicon A mixed vapor deposition material composed of metallic silicon, silicon dioxide, and magnesium oxide mixed so that the number ratio (Mg / Si) was 0.65 was produced. This mixed vapor deposition material was put into a crucible and press-molded so that the bulk density was 1.0 g / cm 3 .
実施例１から２、および、比較例１から２のガスバリア性蒸着フィルムについて、以下の方法で、スプラッシュの発生をチェックし、また、水蒸気透過率を測定評価した。
その結果を表１にまとめた。
About the gas-barrier vapor deposition film of Examples 1 and 2 and Comparative Examples 1 and 2, generation | occurrence | production of the splash was checked with the following method, and the water-vapor-permeation rate was measured and evaluated.
The results are summarized in Table 1.
＜スプラッシュ＞
実施例１から２、および比較例１から２のガスバリア性蒸着フィルム５００ｍｍ幅１００ｍ長について、目視によって、スプラッシュによるピンホールや異物が無いかを調べた。スプラッシュによるピンホールや異物が無い場合を○とし、スプラッシュによるピンホールや異物が１から１０個までを△とし、スプラッシュによるピンホールや異物が１１個以上あるものを×とした。
<Splash>
The gas barrier vapor-deposited films of Examples 1 and 2 and Comparative Examples 1 and 2 were examined visually for the presence of pinholes and foreign matter due to splash by visual inspection. The case where there was no pinhole or foreign matter due to splash was marked as ◯, the number of pinholes or foreign matter due to splash was 1 to 10, and the case where there were 11 or more pinholes or foreign matter due to splash was marked as x.
＜水蒸気透過率＞
実施例１から２、および比較例１から２のガスバリア性蒸着フィルムの水蒸気透過率を水蒸気透過度測定装置（モダンコントロール社製 ＭＯＣＯＮ ＰＥＲＭＡＴＲＡＮ ３／２１）を用いて４０℃９０％ＲＨの雰囲気で測定した。
<Water vapor transmission rate>
The water vapor permeability of the gas barrier vapor deposition films of Examples 1 and 2 and Comparative Examples 1 and 2 was measured in an atmosphere of 40 ° C. and 90% RH using a water vapor permeability measuring device (MOCON PERMATRAN 3/21 manufactured by Modern Control). did.
＜比較結果＞
酸化マグネシウムを蒸着用材料に加えることで顕著な水蒸気バリア性の向上がみられる。金属珪素と二酸化珪素の蒸着用材料からなる蒸着膜の水蒸気透過率が１ｇ／ｍ２・ｄａｙより低いのに対し、酸化マグネシウムを加えた蒸着用材料からなる蒸着膜ではＳｉＯｘとＭｇＯｘの複合膜となることで１ｇ／ｍ２・ｄａｙを超える水蒸気透過率が得られており、本発明の蒸着用材料は水蒸気バリア性が向上したと考えられる。
<Comparison result>
Significant improvement in water vapor barrier properties can be seen by adding magnesium oxide to the deposition material. The vapor transmission rate of the vapor deposition film made of the metal silicon and silicon dioxide vapor deposition material is lower than 1 g / m 2 · day, whereas the vapor deposition film made of the vapor deposition material added with magnesium oxide is composed of a composite film of SiOx and MgOx As a result, a water vapor transmission rate exceeding 1 g / m 2 · day was obtained, and the vapor deposition material of the present invention is considered to have improved water vapor barrier properties.
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