JP5510248B2 - Vapor deposition material - Google Patents
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- JP5510248B2 JP5510248B2 JP2010218577A JP2010218577A JP5510248B2 JP 5510248 B2 JP5510248 B2 JP 5510248B2 JP 2010218577 A JP2010218577 A JP 2010218577A JP 2010218577 A JP2010218577 A JP 2010218577A JP 5510248 B2 JP5510248 B2 JP 5510248B2
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- 238000007740 vapor deposition Methods 0.000 title claims description 92
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical group O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(II) oxide Inorganic materials [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims description 27
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 19
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 17
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- Compositions Of Oxide Ceramics (AREA)
- Physical Vapour Deposition (AREA)
Description
本発明は、食品、医薬品や電子部品等の包装材料として有用な透明ガスバリアフィルムを製造する際に使用する蒸着材料に関する。特に高速成膜可能な電子ビーム（ＥＢ）加熱方式の真空蒸着に最適な酸化スズ系の蒸着材料に関する。 The present invention relates to a vapor deposition material used for producing a transparent gas barrier film useful as a packaging material for foods, pharmaceuticals, electronic parts and the like. More particularly, the present invention relates to a tin oxide-based vapor deposition material that is optimal for electron beam (EB) heating type vacuum vapor deposition capable of high-speed film formation.
食品や医薬品等の包装材料に対しては、内容物の変質を防止することが求められている。例えば、食品用包装材料に対しては、タンパク質や油脂等の酸化や変質を抑制し、更に風味や鮮度を保持できることが求められ、また、無菌状態での取扱が必要とされる医薬品用包装材料に対しては、内容物の有効成分の変質を抑制し、その効能を保持できることが求められている。 For packaging materials such as foods and pharmaceuticals, it is required to prevent the contents from being altered. For example, for food packaging materials, pharmaceutical packaging materials that are required to suppress oxidation and alteration of proteins, fats and oils, and to maintain flavor and freshness, and that require handling in aseptic conditions. Therefore, it is required to suppress the alteration of the active ingredient in the contents and to maintain its efficacy.
ところで、このような内容物の変質は、包装材料を透過する酸素や水蒸気あるいは内容物と反応するような他のガスにより主として引き起こされている。 By the way, such alteration of the contents is mainly caused by oxygen or water vapor that permeates the packaging material or other gas that reacts with the contents.
従って、食品や医薬品等の包装材料に対しては、酸素や水蒸気などのガスを透過させない性質（ガスバリア性）を備えていることが求められており、そのような性質を有する包装材料として、一酸化ケイ素（ＳｉＯ）、ケイ素酸化物（ＳｉＯｘ）、酸化アルミニウム、酸化マグネシウム、酸化スズ等の金属酸化物あるいはこれらの複合酸化物、更には金属フッ化物などのガスバリア性物質を高分子フィルム基材に蒸着させたガスバリア性フィルム材料が知られている。 Accordingly, packaging materials such as foods and pharmaceuticals are required to have properties (gas barrier properties) that do not allow permeation of gases such as oxygen and water vapor. As packaging materials having such properties, A gas barrier material such as silicon oxide (SiO), silicon oxide (SiOx), aluminum oxide, magnesium oxide, tin oxide, or a composite oxide thereof, and further metal fluoride is used as a polymer film substrate. Evaporated gas barrier film materials are known.
また、包装材に透明性が要求される理由としては、内容物の形状や内容物の色などが包装材の外から目視で確認することができ、それにより、内容物の取り違い防止や、損傷の有無、内容物の変質の有無が開封前にわかることが挙げられる。 In addition, as a reason why the packaging material is required to be transparent, the shape of the contents and the color of the contents can be visually confirmed from the outside of the packaging material, thereby preventing the contents from being mixed, The presence or absence of damage and the presence or absence of alteration of the contents can be known before opening.
これらのガスバリアフィルムは真空蒸着法のほかスパッタ法やイオンプレーティング法、ＣＶＤ（Ｃｈｅｍｉｃａｌ Ｖａｐｏｒ Ｄｅｐｏｓｉｔｉｏｎ）法やＡＬＤ（Ａｔｏｍｉｃ Ｌａｙｅｒ Ｄｅｐｏｓｉｔｉｏｎ）法など様々な方法が提案されている。
これらのフィルムは安価に製造されることも求められ、一般にもっとも大きい成膜速度が得られる方式は真空蒸着方式であり、特にＥＢ（ｅｌｅｃｔｒｏｎ ｂｅａｍ）加熱方式によるものが、高い成膜速度が得られ最適である。
中でも高速成膜が可能で安価なフィルムとして、高分子フィルム基材に一酸化ケイ素やＳｉ／ＳｉＯ２混合材料が蒸着されたシリカ系蒸着フィルムや金属アルミを蒸発させて酸素と反応させたいわゆるアルミナ反応蒸着フィルムが、高い透明性と高いガスバリア性、生産性の点とから注目されている。
For these gas barrier films, various methods such as a sputtering method, an ion plating method, a CVD (Chemical Vapor Deposition) method, and an ALD (Atomic Layer Deposition) method have been proposed in addition to the vacuum deposition method.
These films are also required to be manufactured at a low cost. Generally, the method for obtaining the highest film formation rate is a vacuum deposition method, and particularly, the method using an EB (electron beam) heating method can provide a high film formation rate. Is optimal.
Among these, as a low-cost film capable of high-speed film formation, a silica-based vapor-deposited film in which silicon monoxide or a Si / SiO 2 mixed material is vapor-deposited on a polymer film substrate or so-called alumina in which metal aluminum is evaporated and reacted with oxygen Reactive vapor deposition films have attracted attention because of their high transparency, high gas barrier properties, and productivity.
一方近年、食品、医療・医薬品などの包装材料用途以外に、液晶、有機ＥＬなどのフラットパネルディスプレイ用途や太陽電池などのバックシート、フロントシートなどにおいてはより高度のガスバリア性が求められ、さらに長時間の過酷な耐久性試験でも性能が低下しないバリア性が求められている。 On the other hand, in recent years, in addition to packaging materials such as food, medical and pharmaceutical products, flat panel display applications such as liquid crystal and organic EL, and back sheets and front sheets such as solar cells have been required to have higher gas barrier properties. There is a demand for barrier properties that do not degrade the performance even in harsh durability tests.
蒸着膜が単層のシリカ蒸着フィルムやアルミナ反応蒸着フィルムではバリア性が不十分であり多層化などの提案がなされている。またこれらフィルムは高温高湿下保存などの耐久性試験では劣化が見られるなど課題が多い。 A single-layer silica vapor deposition film or an alumina reactive vapor deposition film has insufficient barrier properties, and proposals have been made for multilayering. These films have many problems such as deterioration in durability tests such as storage at high temperature and high humidity.
酸化スズ系のバリアフィルムは、耐久性にも優れ、蒸着層単層でも高いバリア性が期待されているが、透明性や高速成膜性などの課題も多い（特許文献１、２、３）。 A tin oxide-based barrier film is excellent in durability and is expected to have high barrier properties even in a single vapor deposition layer, but has many problems such as transparency and high-speed film forming properties (Patent Documents 1, 2, and 3). .
本発明が解決しようとする課題は、高速成膜可能でバリア性・透明性に優れ、蒸着時のスプラッシュ発生を抑制した蒸着材料を提供し、その蒸着材料を用いたガスバリアフィルムを提供することにある。 The problem to be solved by the present invention is to provide a vapor deposition material that is capable of high-speed film formation, has excellent barrier properties and transparency, suppresses the occurrence of splash during vapor deposition, and provides a gas barrier film using the vapor deposition material. is there.
特許文献１、２には、蒸着で得られた酸化スズ薄膜の組成について記載がされている。特許文献１では酸化スズ薄膜にＳｉなどの無機物として１０重量％以下で物性面に影響しない範囲であれば含有していても良いことが記載されているが、具体的にどの無機物を使用するかは記載されていない。
特許文献１〜３ではスズ薄膜の原料として、金属スズ、一酸化スズ、二酸化スズ単体および混合物が使用可能と記載されているが、実際にどのような組成の原料であるか、蒸着用金属材料の組成そのものについては記載がない。
引用文献２、３は薄膜の製造時に酸素を供給し、反応蒸着を行っている。
Patent Documents 1 and 2 describe the composition of a tin oxide thin film obtained by vapor deposition. Patent Document 1 describes that a tin oxide thin film may be contained as an inorganic substance such as Si as long as it is 10% by weight or less as long as it does not affect the physical properties. Which inorganic substance is specifically used? Is not listed.
In Patent Documents 1 to 3, it is described that metal tin, tin monoxide, tin dioxide alone and a mixture can be used as a raw material for the tin thin film. The composition itself is not described.
In References 2 and 3, oxygen is supplied at the time of manufacturing a thin film, and reactive vapor deposition is performed.
本発明者は、特定の酸化スズ系の蒸着材料が、上述の課題を達成できることを見出し、本発明を完成させるに至った。 The present inventor has found that a specific tin oxide-based vapor deposition material can achieve the above-described problems, and has completed the present invention.
請求項１の発明は、二酸化スズと一酸化スズを主成分とし、酸素とスズの原子比（Ｏ／Ｓｎ比）が１より大きく、１．８未満であり、見掛け密度が１．５〜４．０ｇ／ｃｍ３であることを特徴とする電子ビーム加熱方式用の蒸着材料である。 The invention of claim 1 is mainly composed of tin dioxide and tin monoxide, the atomic ratio of oxygen to tin (O / Sn ratio) is greater than 1 and less than 1.8, and the apparent density is 1.5 to 4 It is a vapor deposition material for an electron beam heating method, characterized by being 0.0 g / cm 3 .
請求項２の発明は、上記蒸着材料はさらに一酸化ケイ素あるいはケイ素と二酸化ケイ素の混合物のいずれかまたは両方を含有し、酸素とスズ＋ケイ素の原子比（Ｏ／（Ｓｉ＋Ｓｎ）比）が１以上１．８以下で、かつ、スズとケイ素の原子比（Ｓｎ／Ｓｉ比）が３以上２０以下であることを特徴とする請求項１記載の蒸着材料である。 According to a second aspect of the present invention, the vapor deposition material further contains one or both of silicon monoxide and a mixture of silicon and silicon dioxide, and an atomic ratio of oxygen to tin + silicon (O / (Si + Sn) ratio) is 1 or more. The vapor deposition material according to claim 1, wherein the vapor deposition material has a atomic ratio of Sn to Si (Sn / Si ratio) of 3 or more and 20 or less, and 1.8 or less.
請求項３の発明は、請求項１または２に記載の蒸着材料を、酸素を供給せずに電子ビーム加熱方式によって、樹脂基材に真空蒸着する、ガスバリアフィルム製造方法である。 Invention of Claim 3 is a gas barrier film manufacturing method which vacuum-deposits the vapor deposition material of Claim 1 or 2 on a resin base material by an electron beam heating system, without supplying oxygen.
請求項４の発明は、ガスバリア層を５００ｎｍ／分〜１２０００ｎｍ／分で成膜する、請求項３に記載のガスバリアフィルム製造方法である。 Invention of Claim 4 is a gas barrier film manufacturing method of Claim 3 which forms a gas barrier layer into a film at 500 nm / min-12000 nm / min.
本発明の蒸着材料は、ＳｎＯ／ＳｎＯ２の混合材料を用い、酸素とスズの原子比Ｏ／Ｓｎを１．０＜（Ｏ／Ｓｎ）＜１．８とすることで、高い蒸発速度を維持しつつ、かつ蒸発にともない発生する分解Ｏ２ガスによる成膜室の真空度の低下や、反応蒸着のように別途酸素を導入する手間や酸素導入による真空度低下もなく、透明で緻密な成膜が可能となり、高いバリア性が発現可能で、スプラッシュ発生を抑制でき、高速成膜を可能にすることができる。 The vapor deposition material of the present invention uses a mixed material of SnO / SnO 2 and maintains a high evaporation rate by setting the oxygen / tin atomic ratio O / Sn to 1.0 <(O / Sn) <1.8. However, there is no reduction in the degree of vacuum in the film formation chamber due to the decomposed O 2 gas generated as a result of evaporation, the trouble of separately introducing oxygen as in reactive vapor deposition, and no reduction in the degree of vacuum due to oxygen introduction. A film can be formed, high barrier properties can be expressed, splash generation can be suppressed, and high-speed film formation can be achieved.
また本発明の蒸発材料はさらに酸化ケイ素などのシリカ系材料を含有することで、高い蒸発速度を得るための高出力のＥＢ照射条件においても、酸化ケイ素と酸化スズの溶融成分が形成されることで、高出力ＥＢ照射条件においてもスプラッシュ現象を抑制することができ、高速成膜を可能にすることができる。 The evaporation material of the present invention further contains a silica-based material such as silicon oxide, so that a molten component of silicon oxide and tin oxide is formed even under high-power EB irradiation conditions for obtaining a high evaporation rate. Thus, the splash phenomenon can be suppressed even under high-power EB irradiation conditions, and high-speed film formation can be achieved.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明の蒸着材料は酸化スズ系の蒸着材料であって、一酸化スズと二酸化スズとを含有し、酸素とスズの原子比（Ｏ／Ｓｎ）が１．０〜１．８であり、見掛け密度が１．５〜４．０ｇ／ｃｍ３である。一酸化スズおよび二酸化スズはいずれも昇華性の材料であって真空蒸着において蒸発材料として優れているが特に本発明の蒸着材料は蒸着材料からのスプラッシュを抑え、かつ蒸発速度を上げることができる。すなわち、一酸化スズと二酸化スズとを含有する蒸着材料の酸素とスズの原子比（Ｏ／Ｓｎ）を１．０〜１．８とし、見掛け密度を１．５〜４．０ｇ／ｃｍ３としたため、スプラッシュが出にくく、かつ高速成膜可能な蒸着速度が得られ、安価で高性能なバリアフィルムを製造することができる。 The vapor deposition material of the present invention is a tin oxide-based vapor deposition material, which contains tin monoxide and tin dioxide, and has an oxygen / tin atomic ratio (O / Sn) of 1.0 to 1.8, which is apparent. The density is 1.5 to 4.0 g / cm 3 . Both tin monoxide and tin dioxide are sublimable materials and are excellent as evaporation materials in vacuum deposition. In particular, the deposition material of the present invention can suppress splash from the deposition material and increase the evaporation rate. That is, the atomic ratio (O / Sn) of oxygen to tin of the vapor deposition material containing tin monoxide and tin dioxide is 1.0 to 1.8, and the apparent density is 1.5 to 4.0 g / cm 3 . Therefore, it is difficult to produce a splash, and a vapor deposition rate capable of forming a film at a high speed is obtained, and an inexpensive and high-performance barrier film can be manufactured.
ここでスプラッシュとは、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などにより、気化していない蒸着材料が、高温の微細な粒のまま飛散する現象である。スプラッシュの発生により、形成された蒸着膜にピンホールが生じてバリアフィルムとしての性能が出なかったり、微細な粒が異物として蒸着原反に混入することも有り得るため、スプラッシュ発生はできるだけ抑制することが好ましい。 Here, the splash is a phenomenon in which a vapor deposition material that is not vaporized is scattered as high-temperature fine particles due to a thermal shock caused by heating during vapor deposition or a pressure of a gas generated from the inside. Due to the occurrence of splash, pinholes may be generated in the formed vapor deposition film, and the performance as a barrier film may not be obtained, or fine particles may be mixed in the vapor deposition raw material as foreign matter, so the occurrence of splash should be suppressed as much as possible. Is preferred.
また、蒸着方式には抵抗加熱方式、誘導加熱方式、電子ビーム方式などある。特に電子ビーム（ＥＢ）方式では蒸着材料を局部的に急速に加熱でき、しかも蒸着材料の堆積速度をはやめ、そのため巻取蒸着加工速度を向上させて包装材料の生産性を高めることができる特徴があり、頻繁に用いられている。しかし電子ビームを直接材料に当てるため、材料が受ける熱衝撃が大きく、スプラッシュが一層発生しやすくなる問題がある。 The vapor deposition method includes a resistance heating method, an induction heating method, an electron beam method, and the like. In particular, the electron beam (EB) method has a feature that the vapor deposition material can be heated locally and rapidly, and the deposition rate of the vapor deposition material can be stopped, so that the winding vapor deposition processing rate can be improved and the productivity of the packaging material can be increased. Yes, it is used frequently. However, since the electron beam is directly applied to the material, there is a problem that the material is subjected to a large thermal shock, and splash is more likely to occur.
なお、本発明の蒸着材料におけるスズと酸素との原子比（Ｏ／Ｓｎ比）は、ＥＤＸ（エネルギー分散型Ｘ線分析装置）により測定することができる。 In addition, the atomic ratio (O / Sn ratio) of tin and oxygen in the vapor deposition material of the present invention can be measured by EDX (energy dispersive X-ray analyzer).
本発明では、少なくとも一酸化スズと二酸化スズとを含有し、スズと酸素との原子比（Ｏ／Ｓｎ比）を１．０〜１．８とし、見掛け密度を１．５〜４．０ｇ／ｃｍ３とすることでスプラッシュの発生を抑えることができる。 In the present invention, at least tin monoxide and tin dioxide are contained, the atomic ratio of tin to oxygen (O / Sn ratio) is 1.0 to 1.8, and the apparent density is 1.5 to 4.0 g / The occurrence of splash can be suppressed by setting it to cm 3 .
酸化スズ系材料を少なくとも２種類混合するのは、各々単独で蒸着材料とするとバリア性、透明性、スプラッシュ、蒸発速度等を制御する点で使用が困難のためである。
一酸化スズ単体では、昇華性物質であるため蒸発速度は速いが、膜の透明性が低下し、所望のバリア性が得られにくい。また一酸化スズは比較的低温で昇華することから、巻き取り蒸着機で高速で大量に蒸発させる際には、緩やかに昇華せずに、材料全体から爆発的に一挙に蒸発し激しいスプラッシュを伴い、高速蒸発には不適である。
二酸化スズ単体では、同じく昇華性であるが、蒸発と同時に分解を伴い酸素ガスが多量に発生し成膜室の真空度が低下して生成されるバリア層のバリア性が低下する。この蒸発特性の異なる酸化スズ系材料を少なくとも２種を合わせることで、透明性、バリア性に優れ、スプラッシュ発生を抑制した、高速蒸発が可能な蒸着材料とした。
The reason why at least two types of tin oxide-based materials are mixed is that it is difficult to use in terms of controlling barrier properties, transparency, splash, evaporation rate, etc., if each is a vapor deposition material.
Since tin monoxide alone is a sublimable substance, the evaporation rate is fast, but the transparency of the film is lowered and it is difficult to obtain a desired barrier property. In addition, since tin monoxide sublimes at a relatively low temperature, when it is vaporized at a high speed by a winding vapor deposition machine at a high speed, it vaporizes from the whole material explosively without accompanying sublimation slowly, accompanied by intense splash. Not suitable for fast evaporation.
Tin dioxide alone is also sublimable, but a large amount of oxygen gas is generated at the same time as evaporation, and the degree of vacuum in the film forming chamber is lowered to lower the barrier property of the generated barrier layer. By combining at least two types of tin oxide-based materials having different evaporation characteristics, a vapor deposition material capable of high-speed evaporation with excellent transparency and barrier properties and suppressed splash generation was obtained.
本発明の蒸着材料は、上記酸化スズ系の材料に加えて、一酸化ケイ素あるいは金属ケイ素と二酸化ケイ素の混合物をさらに加えることができる。
昇華性の材料のみでは、昇華が進み材料残渣がスカスカのスポンジ状になり、スプラッシュの発生が増加することがある。シリカ系の材料を添加することでこの現象を抑制することが可能であることを見出した。すなわち蒸発過程において高温に過熱された材料は酸化スズと酸化ケイ素が反応しシリカ−スズガラスが微量に形成されることでスカスカの材料の溶融バインダーとなり、材料の再結合を促しスポンジ状の部分の発生自体を抑制するため、スプラッシュを抑制することができる。
In addition to the tin oxide-based material, the vapor deposition material of the present invention can further contain silicon monoxide or a mixture of metal silicon and silicon dioxide.
With only a sublimable material, the sublimation proceeds and the material residue becomes a spongy sponge, which may increase the occurrence of splash. It has been found that this phenomenon can be suppressed by adding a silica-based material. In other words, the material heated to a high temperature during the evaporation process reacts with tin oxide and silicon oxide to form a very small amount of silica-tin glass, which becomes a molten binder of the material of Sukasuka and promotes recombination of the material, generating a spongy portion Splash can be suppressed to suppress itself.
添加されるシリカ材料としては、一酸化ケイ素、および混合物が、残渣として過剰に残らず、酸化スズとともに蒸発させることができ適している。特にＳｎ／Ｓｉ（原子比）を３≦（Ｓｎ／Ｓｉ）≦２０とすることで高速蒸発時のスプラッシュを抑制でき好適である。
Ｓｎ／Ｓｉ＞２０ではスプラッシュ抑制効果が少なく、Ｓｎ／Ｓｉ＜３ではガラス相生成が多すぎて、蒸発速度が低下したり、逆に溶融ガラスの突沸などによるスプラッシュが増加するため好ましくない。
As the silica material to be added, silicon monoxide and the mixture are not excessively left as a residue and can be evaporated together with tin oxide, which is suitable. In particular, by setting Sn / Si (atomic ratio) to 3 ≦ (Sn / Si) ≦ 20, it is possible to suppress splash during high-speed evaporation.
When Sn / Si> 20, the effect of suppressing splash is small, and when Sn / Si <3, the glass phase is generated too much, and the evaporation rate is lowered. On the contrary, the splash due to bumping of the molten glass increases, which is not preferable.
酸素とスズの原子比（Ｏ／Ｓｎ比）は混合する粉末の配合量、添加剤等によって調整が可能である。蒸着中においては、酸素とスズの原子比が高いほど脱ガスが多く真空度が低下する。また、酸素とスズの原子比が低いほど真空度は高いが、蒸着された膜が着色して透明性に劣る。また脱ガスが多くてもスプラッシュが出やすい傾向がある。そこで、蒸着材料のＯ／Ｓｎ比は１．０〜１．８の範囲であることが望ましい。同様にシリカ系材料を混合する場合においてもＯ／（Ｓｎ＋Ｓｉ）（原子比）として１．０〜１．８が望ましい。 The atomic ratio of oxygen and tin (O / Sn ratio) can be adjusted by the blending amount of powder to be mixed, additives, and the like. During vapor deposition, the higher the atomic ratio of oxygen and tin, the more outgassing and the lower the degree of vacuum. Further, the lower the atomic ratio of oxygen and tin, the higher the degree of vacuum, but the deposited film is colored and inferior in transparency. Moreover, even if there is much degassing, there is a tendency that splash is likely to occur. Therefore, the O / Sn ratio of the vapor deposition material is desirably in the range of 1.0 to 1.8. Similarly, when mixing silica-based materials, O / (Sn + Si) (atomic ratio) is preferably 1.0 to 1.8.
蒸着材料の見掛け密度は、選択する粉末の粒径のほか、粉末を成形体とする際の製造方法によって調整することができる。水等と混合してスラリー状とする場合は、水分との混合比により調整される。また、プレス法などで押し固める場合は、その圧力により調整される。また、バインダーとして添加剤を用いる場合には、添加剤が空隙に充填される分、密度が高くなる可能性が高い。しかし密度が高すぎると、電子ビームの熱衝撃に対して砕けやすく、また熱伝導性が高い為に材料が暖まりやすく、蒸発の制御がしにくい。逆に密度が低いと、電子ビームの熱衝撃に対して細かく飛び散りやすく、特に脆い場合は、それに加えて壊れやすい為に扱いが難しい。そのため、蒸着材料の見掛け密度は１．５〜４．０ｇ／ｃｍ３であることが望ましい。見掛け密度とは、蒸着材料の材料寸法および重量を測定し、ｇ／ｃｍ３へ単位換算することにより測定された値を意味する。 The apparent density of the vapor deposition material can be adjusted by the manufacturing method when the powder is formed into a molded body, in addition to the particle diameter of the powder to be selected. When mixed with water or the like to form a slurry, it is adjusted by the mixing ratio with water. Moreover, when pressing and hardening by the press method etc., it adjusts with the pressure. Moreover, when using an additive as a binder, there is a high possibility that the density will increase as the additive is filled in the voids. However, if the density is too high, the material is easily broken by the thermal shock of the electron beam, and the material is likely to be warmed due to its high thermal conductivity, making it difficult to control evaporation. On the other hand, if the density is low, it is easy to scatter finely with respect to the thermal shock of the electron beam. Therefore, it is desirable that the apparent density of the vapor deposition material is 1.5 to 4.0 g / cm 3 . An apparent density means the value measured by measuring the material dimension and weight of vapor deposition material, and converting it into g / cm < 3 >.
本発明で製造されるガスバリアフィルムの構成の一例の断面模式図を図１に示す。ガスバリアフィルムは樹脂基材１１の少なくとも片面に、蒸着材料を蒸着した蒸着層（ガスバリア層）１２を有する。本発明のガスバリアフィルムにあっては、酸素とスズの原子比（Ｏ／Ｓｎ比）が１より大きく１．８未満であり、見掛け密度が１．５〜４．０ｇ／ｃｍ３である蒸着材料を用い、樹脂基材に蒸着材料を真空蒸着し、ガスバリア層を形成する蒸着工程によりガスバリア層が形成される。
FIG. 1 shows a schematic cross-sectional view of an example of the configuration of the gas barrier film produced in the present invention. The gas barrier film has a vapor deposition layer (gas barrier layer) 12 in which a vapor deposition material is vapor-deposited on at least one surface of the
本願発明の蒸着材料の原料となる一酸化スズ、二酸化スズ、スズ、一酸化ケイ素、ケイ素と二酸化ケイ素は、市販の粉末状のものを使用できる。
このうちスズに関する原料については次のようなものが使用できる。
粉末の平均粒径は、１００μｍ以下のものが好ましい。
粉末の平均粒径は、１μｍ〜５０μｍのものがさらに好ましい。
平均粒径が１００μｍ以上１μｍ以下では成型体作製容易性や生産性が悪く、またスプラッシュが発生しやすくなるという点から好ましくない。
また、ケイ素に関する原料については、次のようなものが使用できる。
粉末の平均粒径は、７５μｍ以下のものが好ましい。
粉末の平均粒径は、１μｍ〜５０μｍのものがさらに好ましい。
平均粒径が７５μｍ以上、１μｍ以下では成型体などの作製容易性、均一性という点から好ましくない。
原料の純度については請求項１、２の関係を満たしていれば、特に問題とならない。ガスバリア層が所定の性能を満たすような純度の原料を使用すればよい。
Commercially available powders can be used as tin monoxide, tin dioxide, tin, silicon monoxide, silicon and silicon dioxide, which are raw materials for the vapor deposition material of the present invention.
Among these, the following materials can be used for raw materials relating to tin.
The average particle diameter of the powder is preferably 100 μm or less.
The average particle diameter of the powder is more preferably 1 μm to 50 μm.
When the average particle size is 100 μm or more and 1 μm or less, it is not preferable from the viewpoints that the molding ease of production and productivity are poor and splash is likely to occur.
Moreover, the following can be used about the raw material regarding silicon.
The average particle diameter of the powder is preferably 75 μm or less.
The average particle diameter of the powder is more preferably 1 μm to 50 μm.
When the average particle size is 75 μm or more and 1 μm or less, it is not preferable from the viewpoint of the ease of producing a molded body and the uniformity.
The purity of the raw material is not particularly problematic as long as the relations of claims 1 and 2 are satisfied. A raw material having such a purity that the gas barrier layer satisfies a predetermined performance may be used.
真空蒸着法としては、蒸着材料の加熱手段によって抵抗加熱方式、電子ビーム方式、高周波誘導方式、レーザー方式等を選択することができる。中でも、電子ビーム加熱方式の真空蒸着法が熱効率と生産性の点から好ましい。本願発明の蒸着材料を使用する製造装置は、通常使用される電子ビーム加熱方式の真空蒸着装置を使用できる。また、巻き取り装置を備えた前記装置を使用することが生産性の点から好ましい。 As the vacuum evaporation method, a resistance heating method, an electron beam method, a high frequency induction method, a laser method, or the like can be selected depending on the heating means of the evaporation material. Among these, an electron beam heating vacuum deposition method is preferable from the viewpoint of thermal efficiency and productivity. As a manufacturing apparatus using the vapor deposition material of the present invention, a commonly used electron beam heating type vacuum vapor deposition apparatus can be used. Moreover, it is preferable from the point of productivity to use the said apparatus provided with the winding apparatus.
本発明では、樹脂基材への蒸着材料の堆積速度が、５００ｎｍ／分〜１２０００ｎｍ／分の高速成膜でおこなうことが好ましい。本発明の蒸着材料を用いることにより、堆積速度を５００ｎｍ／分以上としても、スプラッシュの発生を抑制することができる。なお、蒸着速度の堆積速度が５００ｎｍ／分に満たない場合にあっては本発明の効果を十分なものとすることができない。一方、堆積速度を１２０００ｎｍ／分とすることは装置上困難である。 In the present invention, the deposition rate of the vapor deposition material on the resin base material is preferably high-speed film formation of 500 nm / min to 12000 nm / min. By using the vapor deposition material of the present invention, the occurrence of splash can be suppressed even when the deposition rate is 500 nm / min or more. In addition, when the deposition rate of vapor deposition rate is less than 500 nm / min, the effect of this invention cannot be made enough. On the other hand, it is difficult for the apparatus to set the deposition rate to 12000 nm / min.
なお、蒸着工程においては、酸素ガスは導入しないことが好ましい。本発明においては、あらかじめ蒸着材料において酸素とスズの原子比（Ｏ／Ｓｎ比）を調整しているため、酸素ガスを導入する必要はない。蒸着工程において酸素ガスを導入しながら真空蒸着を行う場合には、蒸着工程において真空度が低下し透明で緻密な膜が形成されなくなる場合がある。また、製造条件が複雑になる傾向になる。本発明にあっては、蒸着工程において酸素ガスを導入する必要が無く、透明で緻密なガスバリア層を備えるガスバリアフィルムを容易に製造することができる。
電子ビームの出力は、所望の堆積速度になるように調整すればよい。
In the vapor deposition process, it is preferable not to introduce oxygen gas. In the present invention, it is not necessary to introduce oxygen gas because the atomic ratio (O / Sn ratio) of oxygen and tin is previously adjusted in the vapor deposition material. When vacuum vapor deposition is performed while introducing oxygen gas in the vapor deposition step, the degree of vacuum is lowered in the vapor deposition step, and a transparent and dense film may not be formed. In addition, the manufacturing conditions tend to be complicated. In the present invention, it is not necessary to introduce oxygen gas in the vapor deposition step, and a gas barrier film having a transparent and dense gas barrier layer can be easily produced.
What is necessary is just to adjust the output of an electron beam so that it may become a desired deposition rate.
本発明で樹脂基材としては、高分子樹脂からなるフィルム状のものが好ましく、さらに透明性を有することが好ましい。
樹脂基材の種類としては、ガスバリアフィルムとしての目的の物性を実現できるものであれば良い。たとえば、ポリエチレン、ポリプロピレン、ポリアミド、ポリエチレンテレフタレート、ポリエステル、ポリエチレンナフタレート、ポリカーボネート、メチルメタアクリレート、ナイロンが挙げられる。
In the present invention, the resin base material is preferably a film-like material made of a polymer resin, and more preferably transparent.
As a kind of resin base material, what can implement | achieve the target physical property as a gas barrier film should just be sufficient. Examples thereof include polyethylene, polypropylene, polyamide, polyethylene terephthalate, polyester, polyethylene naphthalate, polycarbonate, methyl methacrylate, and nylon.
これらの樹脂基材は、一軸延伸、二軸延伸を行ったものでも良い。また、樹脂の安定化等のために添加物が入っているものでも良い。 These resin base materials may be uniaxially stretched or biaxially stretched. Moreover, the thing containing the additive for resin stabilization etc. may be used.
樹脂基材上には、真空蒸着によりガスバリア層が形成され、ガスバリアフィルムとすることができる。ガスバリア層の膜厚としては、５ｎｍ以上２００ｎｍであることが好ましい。ガスバリア層の膜厚が５ｎｍに満たない場合にあっては、十分なガスバリア性を発揮することができない場合がある。一方、ガスバリア層の膜厚が２００ｎｍを超える場合にあっては成膜後の後加工時にクラックなどが発生しバリア性が劣化する場合がある。 On the resin substrate, a gas barrier layer is formed by vacuum deposition, and a gas barrier film can be obtained. The film thickness of the gas barrier layer is preferably 5 nm or more and 200 nm. If the thickness of the gas barrier layer is less than 5 nm, sufficient gas barrier properties may not be exhibited. On the other hand, when the film thickness of the gas barrier layer exceeds 200 nm, cracks or the like may occur during post-processing after film formation, and the barrier property may deteriorate.
また、本発明のガスバリアフィルムにおいては、さらに、樹脂基材の蒸着面を、蒸着前にコロナ放電処理、低温プラズマ処理などにより、表面の改質を行っても良い。樹脂表面をこのように処理することで、一般的に樹脂と蒸着層の密着性が改良される（向上する）ことが知られている。 In the gas barrier film of the present invention, the surface of the vapor deposition surface of the resin base material may be further modified by corona discharge treatment, low temperature plasma treatment or the like before vapor deposition. It is known that the adhesion between the resin and the vapor deposition layer is generally improved (improved) by treating the resin surface in this manner.
その他にも、樹脂基材と蒸着膜の密着性を良くするために、蒸着前の樹脂基材表面に下塗り層（アンカー層）を塗布・形成することも可能である。 In addition, an undercoat layer (anchor layer) can be applied and formed on the surface of the resin substrate before vapor deposition in order to improve the adhesion between the resin substrate and the vapor deposition film.
樹脂基材に蒸着層を形成したガスバリアフィルムの蒸着層側に、コーティングを施してもよい。また、蒸着層と反対側の樹脂基材面にコーティングを施しても良い。コーティングとは、ヒートシール用のシーラント層やラミネート層などの機能層をも含む。 A coating may be applied to the vapor deposition layer side of the gas barrier film in which the vapor deposition layer is formed on the resin substrate. Moreover, you may coat a resin base material surface on the opposite side to a vapor deposition layer. The coating includes functional layers such as a heat sealant layer and a laminate layer.
これらの下塗り層やコーティングの材料は、目的に適したものを適宜選択して適用することができる。 These undercoat layers and coating materials can be appropriately selected and applied according to the purpose.
以下、本発明を実施例および比較例によりさらに説明するが、本発明は下記例に制限されない。 EXAMPLES Hereinafter, although an Example and a comparative example further demonstrate this invention, this invention is not restrict | limited to the following example.
一酸化スズ粉末（平均粒径１８μｍ）、二酸化スズ粉末（平均粒径４μｍ）をＯ／Ｓｎ比がＯ／Ｓｎ＝１．５となるように混合し、この粉末をアルミナ製ルツボに充填して簡易油圧プレス機にて一軸プレスを施し、電気炉にて１２００℃まで加熱処理を行い、実施例１の蒸着材料である成型体を作製した。
得られた成型体の見掛け密度は２．２ｇ／ｃｍ３であった。
Tin monoxide powder (average particle size 18 μm) and tin dioxide powder (average particle size 4 μm) were mixed so that the O / Sn ratio was O / Sn = 1.5, and this powder was filled in an alumina crucible. A uniaxial press was performed with a simple hydraulic press machine, and a heat treatment was performed up to 1200 ° C. with an electric furnace, so that a molded body as a vapor deposition material of Example 1 was produced.
The apparent density of the obtained molded body was 2.2 g / cm 3 .
実施例１の混合粉末に一酸化ケイ素粉末（平均粒径を１０μｍ）を加え水、シリカゾルバインダー（日産化学製スノーテックスＳＴ−３０）を加えスラリー化して、石膏型に流し込み、キャスト成型後９００℃で焼成しブロック成型体を作製、実施例２の蒸着材料である成形体を得た。 Silicon monoxide powder (average particle size 10 μm) is added to the mixed powder of Example 1, water and silica sol binder (Nissan Chemical Snowtex ST-30) are added to form a slurry, poured into a gypsum mold, and 900 ° C. after cast molding. Was fired to prepare a block molded body, and a molded body as the vapor deposition material of Example 2 was obtained.
実施例２の一酸化ケイ素に変えて金属ケイ素粉末（平均粒径を８μｍ）と二酸化ケイ素（平均粒径１６μｍ）の混合粉末（Ｏ／Ｓｉ＝１．５となるように混合）をＳｎ／Ｓｉ＝１０／１になるように配合し、その他は実施例２と同様にして実施例３の蒸着材料である成形体を得た。 In place of silicon monoxide in Example 2, a mixed powder of metal silicon powder (average particle size of 8 μm) and silicon dioxide (average particle size of 16 μm) (mixed so that O / Si = 1.5) was Sn / Si. = 10/1 was added, and the others were the same as in Example 2 to obtain a molded body as the vapor deposition material of Example 3.
（比較例１）
一酸化スズのみで、実施例１の製造方法により蒸着材料である成型体を作成した。
(Comparative Example 1)
A molded body as a vapor deposition material was prepared by the manufacturing method of Example 1 using only tin monoxide.
（比較例２）
二酸化スズのみで、実施例１の製造方法により蒸着材料である成型体を作成した。
(Comparative Example 2)
A molded body, which is a vapor deposition material, was prepared by the manufacturing method of Example 1 using only tin dioxide.
（評価）
実施例１〜３及び比較例１〜２で作成した蒸着材料について、見掛け密度（かさ密度）を求めた結果を表１に示す。
(Evaluation)
Table 1 shows the results of the apparent density (bulk density) obtained for the vapor deposition materials prepared in Examples 1 to 3 and Comparative Examples 1 and 2.
作成した各材料について、電子ビーム加熱方式の巻き取り式蒸着装置を用いて、実施例及び比較例の蒸着材料を、１２μｍ厚のポリエステルフィルムに、堆積速度１００ｎｍ／分、堆積速度１０００ｎｍ／分で真空蒸着させ、膜厚約５０ｎｍのガスバリアフィルムを得た。
蒸着の際には蒸着装置への酸素供給は行わなかった。
電子ビームの出力は、前記堆積速度になるように調整した。
About each created material, the vapor deposition material of an Example and a comparative example was vacuum-ized by the deposition rate of 100 nm / min and the deposition rate of 1000 nm / min on the 12-micrometer-thick polyester film using the winding-type vapor deposition apparatus of an electron beam heating system. A gas barrier film having a thickness of about 50 nm was obtained by vapor deposition.
During the vapor deposition, oxygen was not supplied to the vapor deposition apparatus.
The output of the electron beam was adjusted so as to achieve the deposition rate.
これらの蒸着の際におけるスプラッシュ発生の有無、程度を成膜中に蒸着装置内部を観察することにより目視で確認した。
以下に評価基準を示す。
二重丸（◎）印：スプラッシュ発生がほとんど見られなかった
丸（○）印 ：スプラッシュ発生がわずかに見られた
三角（△）印 ：スプラッシュ発生がやや多く見られた
バツ（×）印 ：スプラッシュ発生が頻繁に見られた
なお、成膜中にスプラッシュが発生したバリアフィルムにおいては、スプラッシュの程度に比例して光学的な欠陥検査装置を用いたピンホール検査でガスバリアフィルムにピンホールが確認された。
The presence / absence of the occurrence of splash during the vapor deposition and the degree thereof were visually confirmed by observing the inside of the vapor deposition apparatus during film formation.
The evaluation criteria are shown below.
Double circle (◎): Splash was hardly observed. Circle (○): Splash was slightly observed. Triangle (△): Splash was slightly observed. X (x): Splash was frequently observed. In the barrier film where splash occurred during film formation, pinholes were confirmed in the gas barrier film by pinhole inspection using an optical defect inspection device in proportion to the degree of splash. It was done.
次に、得られたガスバリアフィルムの水蒸気透過度（ｇ／ｍ２・ｄａｙ）を水蒸気透過度測定装置（ＰＥＲＭＡＴＲＡＮ ３／３０、ｍｏｃｏｎ社製）にて４０℃、９０％ＲＨの雰囲気下で測定した。なお、ガスバリアフィルムの水蒸気透過度の測定にあっては、スプラッシュによるガスバリア層のピンホールの発生箇所を除いた部分において測定をおこなっている。
水蒸気透過度は値が低いほど、ガスバリア性が良いことを示す。
得られた結果を表１に示す。
Next, the water vapor permeability (g / m 2 · day) of the obtained gas barrier film was measured with a water vapor permeability measuring device (PERMATRAN 3/30, manufactured by mocon) in an atmosphere of 40 ° C. and 90% RH. . In the measurement of the water vapor permeability of the gas barrier film, the measurement is performed in a portion excluding the occurrence of pinholes in the gas barrier layer due to splash.
The lower the value of the water vapor transmission rate, the better the gas barrier property.
The obtained results are shown in Table 1.
また、得られたガスバリアフィルムの透過率を分光光度計ＵＶ３１００にて測定し３５０ｎｍ、５５０ｎｍにおける透過率を表１に示す。
３５０ｎｍは、生成した酸化スズ膜が黄色に着色していないかを確認するために測定した。５５０ｎｍは可視光の中心波長として、透明性の判断のために測定した。
Further, the transmittance of the obtained gas barrier film was measured with a spectrophotometer UV3100, and the transmittance at 350 nm and 550 nm is shown in Table 1.
350 nm was measured in order to confirm whether the produced tin oxide film was colored yellow. 550 nm was measured as the center wavelength of visible light for the purpose of determining transparency.
表１及び製造方法からわかるように、実施例１〜３の蒸着材料はいずれも、高速成膜時においてもスプラッシュ発生が抑制され、透明性が高く、ガスバリア性の良好なガスバリアフィルムを製造できる蒸着材料であった。
一方、比較例１の一酸化スズのみの蒸着材料はスプラッシュが発生しやすく、また透明性に劣り、比較例２の二酸化スズのみの蒸着材料は高速では真空度が低下してバリア性が低下するとともに、スプラッシュも激しくなり不適であった。
比較例１、２の蒸着材料で成膜したガスバリアフィルムは、３５０ｎｍでの透過率、ガスバリア性（水蒸気透過度）が、実施例１〜３に比べて悪いものであった。特に比較例１、２での高速成膜では、スプラッシュが多く発生し、蒸着膜の不良だけでなく、樹脂基材までもがスプラッシュで損傷を受けていた。
As can be seen from Table 1 and the production method, all of the vapor deposition materials of Examples 1 to 3 are vapor depositions capable of producing a gas barrier film that suppresses the occurrence of splash even during high-speed film formation, has high transparency, and has good gas barrier properties. It was a material.
On the other hand, the vapor deposition material of only the tin monoxide of the comparative example 1 is likely to generate splash and is inferior in transparency, and the vapor deposition material of only the tin dioxide of the comparative example 2 has a reduced vacuum degree and a barrier property at a high speed. At the same time, the splash became intense and unsuitable.
The gas barrier films formed with the vapor deposition materials of Comparative Examples 1 and 2 had poorer transmittance and gas barrier properties (water vapor permeability) at 350 nm than those of Examples 1 to 3. In particular, in the high-speed film formation in Comparative Examples 1 and 2, a lot of splash occurred, and not only the defect of the deposited film but also the resin base material was damaged by the splash.
１１ 樹脂基材
１２ 蒸着層
11
Claims (4)
酸素とスズ＋ケイ素の原子比（Ｏ／（Ｓｉ＋Ｓｎ）比）が１以上１．８以下で、かつ、
スズとケイ素の原子比（Ｓｎ／Ｓｉ比）が３以上２０以下であることを特徴とする請求項１記載の蒸着材料。 The vapor deposition material further contains either or both of silicon monoxide and a mixture of silicon and silicon dioxide,
The atomic ratio of oxygen and tin + silicon (O / (Si + Sn) ratio) is 1 or more and 1.8 or less, and
The vapor deposition material according to claim 1, wherein the atomic ratio of tin to silicon (Sn / Si ratio) is 3 or more and 20 or less.
請求項１または２に記載の蒸着材料を、酸素を供給せずに電子ビーム加熱方式によって樹脂基材に真空蒸着し、ガスバリア層を形成する蒸着工程を備えることを特徴とするガスバリアフィルム製造方法。 A method for producing a gas barrier film comprising a gas barrier layer on at least one surface of a resin substrate,
A gas barrier film manufacturing method comprising: a vapor deposition step of forming a gas barrier layer by vacuum vapor deposition of the vapor deposition material according to claim 1 or 2 on a resin base material by an electron beam heating method without supplying oxygen.
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