JP2011184729A - Vapor deposition material, and method for producing the same - Google Patents
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- 239000000463 material Substances 0.000 title claims abstract description 83
- 238000007740 vapor deposition Methods 0.000 title claims abstract description 66
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000008859 change Effects 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 238000010304 firing Methods 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000011863 silicon-based powder Substances 0.000 claims description 8
- 238000010894 electron beam technology Methods 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 238000005245 sintering Methods 0.000 abstract description 4
- 239000002002 slurry Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 238000000151 deposition Methods 0.000 description 11
- 239000005022 packaging material Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- 230000008021 deposition Effects 0.000 description 9
- 230000004888 barrier function Effects 0.000 description 7
- 238000005259 measurement Methods 0.000 description 6
- 229920006254 polymer film Polymers 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 229910052814 silicon oxide Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 238000007088 Archimedes method Methods 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 230000004075 alteration Effects 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000004455 differential thermal analysis Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000011129 pharmaceutical packaging material Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- -1 polysiloxane Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
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- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
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- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
本発明は、食品や医薬品等の包装材料として有用な、ガスバリア性ケイ素酸化物蒸着層を有する包装材料を製造する際に使用する蒸着材料およびその製造方法に関する。 TECHNICAL FIELD The present invention relates to a vapor deposition material used when producing a packaging material having a gas barrier silicon oxide vapor deposition layer, which is useful as a packaging material for foods and pharmaceuticals, and a method for producing the vapor deposition material.
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、アルミニウムなどの金属、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が、中でも高分子フィルム基材に一酸化ケイ素が蒸着された材料が、高い透明性と高いガスバリア性の点とから注目されている。 Accordingly, packaging materials such as foods and pharmaceuticals are required to have a property (gas barrier property) that does not allow permeation of gases such as oxygen and water vapor. As a packaging material having such properties, aluminum is required. Polymer film bases such as metals such as silicon monoxide (SiO), silicon oxide (SiOx), metal oxides such as aluminum oxide and magnesium oxide or composite oxides thereof, and further metal fluorides A gas barrier film material deposited on a material is known, and among them, a material obtained by depositing silicon monoxide on a polymer film substrate has attracted attention because of its high transparency and high gas barrier property.
このような一酸化ケイ素が蒸着されたフィルム材料は、蒸着材料である一酸化ケイ素を抵抗加熱法により高分子フィルムに真空蒸着させることにより製造されているが、ここで用いられている蒸着材料の一酸化ケイ素等のケイ素酸化物は、ＳｉとＳｉＯ２とを原料として真空蒸着法により製造されているために、以下に示すような欠点を有している。 Such a film material on which silicon monoxide is deposited is manufactured by vacuum-depositing silicon monoxide, which is a deposition material, on a polymer film by a resistance heating method. Since silicon oxides such as silicon monoxide are produced by vacuum deposition using Si and SiO2 as raw materials, they have the following drawbacks.
真空蒸着法により製造された一酸化ケイ素等の蒸着材料は真密度に非常に近い密度を有し、非常に緻密な構造となっている。このため、この蒸着材料を蒸着させてフィルム材料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（スプラッシュ現象）が生じやすいという問題がある。このような高温の微細粒が蒸着基材である高分子フィルムに衝突した場合には、一酸化ケイ素などの蒸着材料の蒸着により形成した薄膜にピンホールが生じてガスバリア性が低下するという問題や、蒸着材料の蒸着により形成した薄膜を有する包装材料をロールに巻き取る際に、その微細粒が包装材料の間に巻取られ、最終的に製品中に混入するという問題もある。また、場合により高分子フィルム基材に貫通孔を生じさせるという問題も生じる。 A vapor deposition material such as silicon monoxide manufactured by a vacuum vapor deposition method has a density very close to the true density and has a very dense structure. For this reason, when a film material is manufactured by vapor deposition of this vapor deposition material, the vaporized vapor deposition material that has not been vaporized due to the thermal shock caused by heating during vapor deposition or the pressure of gas generated from the inside becomes a high-temperature fine structure. There is a problem that the phenomenon of splashing in the form of grains (splash phenomenon) is likely to occur. When such high-temperature fine particles collide with a polymer film that is a vapor deposition base material, pinholes are generated in a thin film formed by vapor deposition of a vapor deposition material such as silicon monoxide and the gas barrier property is lowered. Further, when a packaging material having a thin film formed by vapor deposition of a vapor deposition material is wound on a roll, the fine particles are wound between the packaging materials and finally mixed into the product. Moreover, the problem that a through-hole is produced in a polymer film base material also arises by the case.
また、近年では、坩堝や加熱ヒーターなどを使用する従来の抵抗加熱蒸着法に代えて、蒸着材料を局部的且つ急速に加熱でき、しかも包装材料の生産性を高めるために蒸着材料の堆積速度を速めて巻取蒸着加工速度を向上させることのできる電子ビーム加熱蒸着法が採用される傾向があるが、この電子ビーム加熱蒸着法の場合、抵抗加熱蒸着法の場合に比べ、蒸着材料が受ける熱衝撃のレベルが格段と高くなるので、上記の問題がいっそう顕著に現れるようになる。 In recent years, instead of the conventional resistance heating vapor deposition method using a crucible or a heater, the vapor deposition material can be heated locally and rapidly, and the deposition rate of the vapor deposition material is increased in order to increase the productivity of the packaging material. There is a tendency to adopt an electron beam heating vapor deposition method that can speed up and improve the winding vapor deposition processing speed, but in this electron beam heating vapor deposition method, the heat received by the vapor deposition material is higher than in the resistance heating vapor deposition method. Since the level of impact is significantly higher, the above problem becomes more prominent.
そこで、従来、このような問題を解決するために、例えば、一酸化ケイ素を高分子フィルム基材に蒸着させる場合、蒸着材料（ＳｉＯ）を真空蒸着法により予めＳｉとＳｉＯ２とから製造しておくのではなく、ＳｉとＳｉＯ２とを乾式で混合して加圧成形し焼結したものを蒸着材料とすることが提案されている（特許文献１）。 Therefore, conventionally, in order to solve such a problem, for example, when silicon monoxide is deposited on a polymer film substrate, a deposition material (SiO) is previously produced from Si and SiO 2 by a vacuum deposition method. Instead, it is proposed that Si and SiO 2 are mixed in a dry manner, pressure-molded and sintered to be a deposition material (Patent Document 1).
この方法によれば、焼結法を利用しているために比較的低コストで製造できるが、生産性を向上させる目的で電子ビームの出力レベルを従来以上にあげた場合、十分な程度にまでスプラッシュ現象を抑制することができないという問題があった。 According to this method, since the sintering method is used, it can be manufactured at a relatively low cost. However, when the output level of the electron beam is increased more than before for the purpose of improving the productivity, it is sufficiently high. There was a problem that the splash phenomenon could not be suppressed.
そこで、Ｓｉ粉末とＳｉＯ２粉末とを含有するスラリーを湿式成形し、その成形の際にゲル化させ、得られた成形体を乾燥し、焼成する多孔質蒸着材料が提案されている（特許文献２）。 Therefore, a porous vapor deposition material has been proposed in which a slurry containing Si powder and SiO 2 powder is wet-molded, gelled during the molding, and the resulting molded body is dried and fired (patent document). 2).
焼成温度が低すぎると成型体にＯＨ基が多く残り、その残存ＯＨ基がスプラッシュの一因となると考えられる。 If the firing temperature is too low, it is considered that many OH groups remain in the molded body, and the residual OH groups contribute to splash.
本発明の目的は、スプラッシュの発生を顕著に抑制できる、水を用いて成型した蒸着材料及びその製造方法を提供することにある。 The objective of this invention is providing the vapor deposition material shape | molded using water which can suppress generation | occurrence | production of a splash remarkably, and its manufacturing method.
本発明者は、焼成条件を最適化することにより製造された蒸着材料が、上述の目的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 the vapor deposition material produced by optimizing the firing conditions can achieve the above-described object, and has completed the present invention.
すなわち、本発明は、水を用いて成型した、一酸化ケイ素粉末を含有する蒸着材料において、焼成条件を最適化することにより、強熱減量（物質を強熱（６００±２５℃２時間）したときの質量の減少量）での重量変化率が１％以下である蒸着材料を提供する。 That is, according to the present invention, a vapor loss material containing silicon monoxide powder molded with water is used to reduce the ignition loss (substance is ignited (600 ± 25 ° C. for 2 hours) by optimizing the firing conditions. And a deposition material having a weight change rate of 1% or less.
また、本発明は、成型体を焼成する工程での焼成条件が大気雰囲気であり、かつ焼成温度が２００℃以上７００℃以下である蒸着材料の製造方法を提供する。 Moreover, this invention provides the manufacturing method of the vapor deposition material whose baking conditions in the process of baking a molded object are air | atmosphere atmosphere, and whose baking temperature is 200 degreeC or more and 700 degrees C or less.
本発明の蒸着材料は、強熱減量（物質を強熱（６００±２５℃２時間）したときの質量の減少量）での重量変化率が１％以下であることにより、スプラッシュの発生を顕著に抑制できる。 In the vapor deposition material of the present invention, the occurrence of splash is noticeable when the weight change rate is 1% or less at the loss on ignition (the amount of decrease in mass when the substance is heated at high temperature (600 ± 25 ° C. for 2 hours)). Can be suppressed.
本発明の蒸着材料の製造方法は、焼成条件を最適化することにより、強熱減量（物質を強熱（６００±２５℃２時間）したときの質量の減少量）での重量変化率が１％以下である蒸着材料を製造でき、これによりスプラッシュの発生を顕著に抑制できる。 In the method for producing a vapor deposition material according to the present invention, the weight change rate at a loss on ignition (a reduction in mass when a substance is ignited (600 ± 25 ° C. for 2 hours)) is 1 by optimizing the firing conditions. % Or less of vapor deposition material can be produced, and the occurrence of splash can be remarkably suppressed.
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一酸化ケイ素を主体とする蒸着材料で、水を用いて成型される。水を用いて成型した蒸着材料は、そのままでは材料内部に残存するＯＨ基によりスプラッシュ現象が生じる。そこで、焼成による脱ＯＨ化を検討した。十分に焼成が行われると残存ＯＨ基はなくなるため、強熱減量（物質を強熱（６００±２５℃２時間）したときの質量の減少量）での重量変化率が１％以下となり、スプラッシュ現象が抑制されたものとなる。 The vapor deposition material of the present invention is a vapor deposition material mainly composed of silicon monoxide, and is molded using water. A vapor deposition material molded using water causes a splash phenomenon due to OH groups remaining in the material as it is. Therefore, deOHization by firing was examined. Since residual OH groups disappear after sufficient firing, the weight change rate with a loss on ignition (a decrease in mass when the substance is ignited (600 ± 25 ° C. for 2 hours)) is 1% or less, and splash. The phenomenon is suppressed.
また、本発明の蒸着材料の成型体を焼成する工程において、材料の酸化による膨張率は、１％以上３％以下である。材料の酸化による膨張率が１％未満であると、材料が十分に酸化されないために、蒸着に際して適度な溶融相が生成されず、スプラッシュの原因になるおそれがある。材料の酸化による膨張率が３％を超えると、膨張しすぎるために、材料にひび割れが生じるなど、使用性に支障をきたすおそれがある。 Further, in the step of firing the molded body of the vapor deposition material of the present invention, the expansion coefficient due to the oxidation of the material is 1% or more and 3% or less. If the expansion coefficient due to the oxidation of the material is less than 1%, the material is not sufficiently oxidized, so that an appropriate molten phase is not generated during vapor deposition, which may cause splash. If the expansion rate due to the oxidation of the material exceeds 3%, the material expands too much, and the material may be cracked.
本発明の蒸着材料を構成する物質（原料）としては、一酸化ケイ素又は金属ケイ素、二酸化ケイ素を使用することができる。なかでも、金属ケイ素と二酸化ケイ素とを原料として構成されたものが、ガスバリア性に優れたＳｉＯ膜を形成できるので好ましい。 As a substance (raw material) constituting the vapor deposition material of the present invention, silicon monoxide, silicon metal, or silicon dioxide can be used. Among these, those composed of metal silicon and silicon dioxide as raw materials are preferable because an SiO film having excellent gas barrier properties can be formed.
なお、これらの一酸化ケイ素又は金属ケイ素、二酸化ケイ素は、粉末状で使用することが好ましく、平均粒径は一般に１μｍ以上２０μｍ以下のものが好ましい。１μｍよりも細かい粒子や、２０μｍよりも大きい粒子では、材料が作りづらく、スプラッシュが多くなるので好ましくない。また、一酸化ケイ素粉末の平均粒径は５μｍ以上１０μｍ以下、金属ケイ素粉末の平均粒径は５μｍ以上１５μｍ以下、二酸化ケイ素粉末の平均粒径は３μｍ以上１０μｍ以下のものが特に好ましい。主として、一酸化ケイ素粉末を使用するが、金属ケイ素粉末と二酸化ケイ素粉末のいずれか又は両方を原料として使用することもできる。その場合の混合比率は、重量％で３０％以上の一酸化ケイ素粉末を使用し、金属ケイ素粉末と二酸化ケイ素粉末をモル比で１：１から１：５に混合したものがスプラッシュを抑制できるので好ましい。より好ましくは、金属ケイ素粉末と二酸化ケイ素粉末をモル比で１：１．５に混合したものが特に好ましい。 In addition, it is preferable to use these silicon monoxide or metal silicon, and silicon dioxide in a powder form, and generally an average particle diameter of 1 micrometer or more and 20 micrometers or less is preferable. Particles finer than 1 μm and particles larger than 20 μm are not preferable because the material is difficult to make and the splash increases. The average particle size of the silicon monoxide powder is 5 μm to 10 μm, the average particle size of the metal silicon powder is 5 μm to 15 μm, and the average particle size of the silicon dioxide powder is particularly preferably 3 μm to 10 μm. Although silicon monoxide powder is mainly used, either or both of metal silicon powder and silicon dioxide powder can be used as a raw material. In this case, the mixture ratio is 30% or more by weight%, and a mixture of metal silicon powder and silicon dioxide powder in a molar ratio of 1: 1 to 1: 5 can suppress splash. preferable. More preferably, a metal silicon powder and a silicon dioxide powder are mixed in a molar ratio of 1: 1.5.
本発明の蒸着材料は、一酸化ケイ素の粉末を含有するスラリーを湿式成形し、その成形の際にゲル化させ、得られた成形物を乾燥し焼成することを特徴とする蒸着材料の製造方法により製造することができる。 The vapor deposition material of the present invention is a method for producing a vapor deposition material, characterized in that a slurry containing silicon monoxide powder is wet-molded, gelled during the molding, and the resulting molded product is dried and fired. Can be manufactured.
本発明の製造方法においては、まず、上述のような一酸化ケイ素の粉末を含有するスラリーを常法に従って調製する。ここで、スラリー化する際に使用する媒体としては、水、アルコールあるいはこれらの混合媒体を使用することができる。 In the production method of the present invention, first, a slurry containing the above-mentioned silicon monoxide powder is prepared according to a conventional method. Here, water, alcohol, or a mixed medium thereof can be used as a medium used for slurrying.
次に、得られたスラリーを湿式成形法により成形するが、この成形の際にスラリーをゲル化させることが必要である。なお、スラリーの調整に際しては、原料粒子の大きさ、使用量、媒体の量と種類、ゲル化時間等を適宜調整して、形成される蒸着材料の嵩密度を調整することが好ましい。 Next, although the obtained slurry is shape | molded by the wet shaping | molding method, it is necessary to gelatinize a slurry in the case of this shaping | molding. When adjusting the slurry, it is preferable to adjust the bulk density of the vapor deposition material to be formed by appropriately adjusting the size of the raw material particles, the amount used, the amount and type of the medium, the gelation time, and the like.
また、スラリーのゲル化を行う際に、無機バインダーを使用することができるが、シリカゾルやテトラエトキシシランなどを使用することが特に好ましい。これにより、塩基性アルカリ金属化合物を使用することなく低温下で原料粉末を十分に結合させることができる。特に、金属ケイ素粉末を使用した場合には、それらのバインダーが金属の表面を保護する機能を有するので、大気雰囲気中での焼成も可能となり、より製造コストを下げることができる。 In addition, an inorganic binder can be used when gelling the slurry, but it is particularly preferable to use silica sol or tetraethoxysilane. Thereby, raw material powder can be fully combined under low temperature, without using a basic alkali metal compound. In particular, when metal silicon powder is used, since these binders have a function of protecting the metal surface, firing in an air atmosphere is also possible, and the manufacturing cost can be further reduced.
なお、シリカゾルによるゲル化は、スラリーに塩酸などの酸を添加してゾルを不安定化することにより行うことができる。また、テトラエトキシシランによるゲル化は、テトラエトキシシランの加水分解と競争的に生じる重縮合がポリシロキサンを形成することにより行うことができる。 Gelation with silica sol can be performed by adding an acid such as hydrochloric acid to the slurry to destabilize the sol. Further, the gelation with tetraethoxysilane can be carried out by forming polysiloxane by polycondensation that occurs competitively with the hydrolysis of tetraethoxysilane.
次に、ゲル化した成形物を乾燥し、大気雰囲気で２００℃以上７００℃以下程度の温度で焼成する。なお、大気雰囲気以外の焼成では、適度な酸化状態が得られず、スプラッシュが発生するので好ましくない。これにより、本発明の蒸着材料が得られる。 Next, the gelled molded product is dried and fired at a temperature of about 200 ° C. to 700 ° C. in an air atmosphere. Note that firing in an atmosphere other than the air atmosphere is not preferable because a proper oxidation state cannot be obtained and splash is generated. Thereby, the vapor deposition material of this invention is obtained.
このようにして得られる本発明の蒸着材料は、従来の蒸着材料と同様に真空蒸着法に適用することができるが、特に従来の蒸着材料に対してスプラッシュ現象を抑制することが困難であった電子ビーム加熱蒸着法に対しても、スプラッシュ現象を生じさせることなく適用することができる。 The vapor deposition material of the present invention thus obtained can be applied to the vacuum vapor deposition method in the same manner as the conventional vapor deposition material, but it has been difficult to suppress the splash phenomenon particularly with respect to the conventional vapor deposition material. The present invention can also be applied to the electron beam heating vapor deposition method without causing a splash phenomenon.
以下、本発明の蒸着材料及びその製造方法の有効性を比較材料と対比することにより具体的に説明する。 Hereinafter, the effectiveness of the vapor deposition material of the present invention and the manufacturing method thereof will be specifically described by comparing with comparative materials.
［ 実施例１・２ ］
主として、平均粒径が７μｍの一酸化ケイ素粉末を重量％で３０％以上使用し、さらに、平均粒径が１０μｍの金属ケイ素粉末、平均粒径が６μｍの二酸化ケイ素粉末を、Ｏ／Ｓｉ比が１．１２となるように混合し（実施例１）、またはＯ／Ｓｉ比が１．１４となるように混合し（実施例２）、水を用いてスラリーを調製し、シリカゾルと塩酸を加えた。
[Examples 1 and 2]
Mainly, a silicon monoxide powder having an average particle diameter of 7 μm is used in an amount of 30% or more by weight, and further, a metal silicon powder having an average particle diameter of 10 μm and a silicon dioxide powder having an average particle diameter of 6 μm are used. Mix so as to be 1.12. (Example 1) or mix so that the O / Si ratio is 1.14 (Example 2), prepare a slurry using water, add silica sol and hydrochloric acid. It was.
次に、このスラリーを型に流し込み、数時間放置して十分にゲル化した。このゲル化物を乾燥した後、１０℃／分の速度で６００℃まで昇温し、６００℃で１時間焼成することにより実施例１及び２の蒸着材料を得た。得られた蒸着材料の嵩密度をアルキメデス法にて測定した。また、ＪＩＳ Ｚ ２２４６に準拠してショアー硬さを測定した。また、エスアイアイ・ナノテクノロジー（株）製ＴＧ／ＤＴＡ６２００示差熱熱重量同時測定装置を用いて重量変化率を測定した。示差熱熱重量同時測定とは、熱重量測定と示差熱分析とを組み合わせて、単一の装置で同時に測定する方法である。具体的には、１０５±５℃で２時間乾燥し、材料吸着水を取り除いた後、６００±２５℃で２時間、窒素雰囲気下で行い、強熱減量（物質を強熱（６００±２５℃２時間）したときの質量の減少量）での重量変化率を求めた。その結果を表１に示す。 Next, this slurry was poured into a mold and allowed to stand for several hours to sufficiently gel. After the gelled product was dried, the temperature was raised to 600 ° C. at a rate of 10 ° C./min, and baked at 600 ° C. for 1 hour to obtain the vapor deposition materials of Examples 1 and 2. The bulk density of the obtained vapor deposition material was measured by the Archimedes method. Moreover, Shore hardness was measured based on JISZ2246. Further, the weight change rate was measured using a TG / DTA6200 differential thermogravimetric simultaneous measurement device manufactured by SII Nano Technology. The differential thermothermal gravimetric simultaneous measurement is a method in which thermogravimetry and differential thermal analysis are combined and measured simultaneously with a single device. Specifically, after drying at 105 ± 5 ° C. for 2 hours and removing the material adsorbed water, it was performed at 600 ± 25 ° C. for 2 hours in a nitrogen atmosphere, and the ignition loss (substance was ignited (600 ± 25 ° C. The weight change rate at the time of 2 hours) was determined. The results are shown in Table 1.
［ 比較例１ ］
焼成温度が１２０℃であること以外は実施例１と同様にスラリーを調製し、比較例１の材料を得た。得られた蒸着材料の嵩密度をアルキメデス法にて測定した。また、ＪＩＳ Ｚ ２２４６に準拠してショアー硬さを測定した。また、エスアイアイ・ナノテクノロジー（株）製ＴＧ／ＤＴＡ６２００示差熱熱重量同時測定装置を用いて重量変化率を測定した。示差熱熱重量同時測定とは、熱重量測定と示差熱分析とを組み合わせて、単一の装置で同時に測定する方法である。具体的には、１０５±５℃で２時間乾燥し、材料吸着水を取り除いた後、６００±２５℃で２時間、窒素雰囲気下で行い、強熱減量（物質を強熱（６００±２５℃２時間）したときの質量の減少量）での重量変化率を求めた。その結果を表１に示す。
[Comparative Example 1]
A slurry was prepared in the same manner as in Example 1 except that the firing temperature was 120 ° C., and the material of Comparative Example 1 was obtained. The bulk density of the obtained vapor deposition material was measured by the Archimedes method. Moreover, Shore hardness was measured based on JISZ2246. Further, the weight change rate was measured using a TG / DTA6200 differential thermogravimetric simultaneous measurement device manufactured by SII Nano Technology. The differential thermothermal gravimetric simultaneous measurement is a method in which thermogravimetry and differential thermal analysis are combined and measured simultaneously with a single device. Specifically, after drying at 105 ± 5 ° C. for 2 hours and removing the material adsorbed water, it was performed at 600 ± 25 ° C. for 2 hours in a nitrogen atmosphere, and the ignition loss (substance was ignited (600 ± 25 ° C. The weight change rate at the time of 2 hours) was determined. The results are shown in Table 1.
［ 比較例２〜４ ］
また、焼成温度が８００℃であること以外は実施例２と同様にスラリーを調製し、比較例２の材料を得た。また、焼成温度が１０００℃であること以外は実施例２と同様にスラリーを調製し、比較例３の材料を得た。また、焼成温度が１５００℃であること以外は実施例２と同様にスラリーを調製し、比較例４の材料を得た。得られた蒸着材料の嵩密度をアルキメデス法にて測定した。また、ＪＩＳ Ｚ ２２４６に準拠してショアー硬さを測定した。また、エスアイアイ・ナノテクノロジー（株）製ＴＧ／ＤＴＡ６２００示差熱熱重量同時測定装置を用いて重量変化率を測定した。示差熱熱重量同時測定とは、熱重量測定と示差熱分析とを組み合わせて、単一の装置で同時に測定する方法である。具体的には、１０５±５℃で２時間乾燥し、材料吸着水を取り除いた後、６００±２５℃で２時間、窒素雰囲気下で行い、強熱減量（物質を強熱（６００±２５℃２時間）したときの質量の減少量）での重量変化率を求めた。その結果を表１に示す。
[Comparative Examples 2 to 4]
A slurry was prepared in the same manner as in Example 2 except that the firing temperature was 800 ° C., and the material of Comparative Example 2 was obtained. A slurry was prepared in the same manner as in Example 2 except that the firing temperature was 1000 ° C., and the material of Comparative Example 3 was obtained. A slurry was prepared in the same manner as in Example 2 except that the firing temperature was 1500 ° C., and the material of Comparative Example 4 was obtained. The bulk density of the obtained vapor deposition material was measured by the Archimedes method. Moreover, Shore hardness was measured based on JISZ2246. Further, the weight change rate was measured using a TG / DTA6200 differential thermogravimetric simultaneous measurement device manufactured by SII Nano Technology. The differential thermothermal gravimetric simultaneous measurement is a method in which thermogravimetry and differential thermal analysis are combined and measured simultaneously with a single device. Specifically, after drying at 105 ± 5 ° C. for 2 hours and removing the material adsorbed water, it was performed at 600 ± 25 ° C. for 2 hours in a nitrogen atmosphere, and the ignition loss (substance was ignited (600 ± 25 ° C. The weight change rate at the time of 2 hours) was determined. The results are shown in Table 1.
［ 評価 ］
電子ビーム加熱方式のバッチ式蒸着装置を用いて、実施例１・２及び比較例１〜４の蒸着材料を真空蒸着した。これらの蒸着材料を蒸着した際のスプラッシュ現象の有無を、目視にて観察し、表１に示した評価基準に従って評価した。その結果を表１に示す。
[Evaluation]
The deposition materials of Examples 1 and 2 and Comparative Examples 1 to 4 were vacuum deposited using an electron beam heating batch deposition apparatus. The presence or absence of a splash phenomenon when these vapor deposition materials were vapor-deposited was visually observed and evaluated according to the evaluation criteria shown in Table 1. The results are shown in Table 1.
表１から、実施例１・２の蒸着材料は、非常に高い蒸発速度（電子ビームの出力レベルが高い場合）で蒸着された場合でも、スプラッシュ現象は観察されなかった。 From Table 1, no splash phenomenon was observed even when the deposition materials of Examples 1 and 2 were deposited at a very high evaporation rate (when the output level of the electron beam was high).
一方、比較例１の蒸着材料は、焼成温度が低すぎるために、強熱減量での重量変化率が１％を超え、残存ＯＨ基が多量に存在するため、スプラッシュ現象が観察された。さらに、材料が十分に酸化されず、蒸着に際して適度な溶融相が生成されなかったため、スプラッシュ現象が観察された。 On the other hand, in the vapor deposition material of Comparative Example 1, since the firing temperature was too low, the weight change rate with loss on ignition exceeded 1%, and a large amount of residual OH groups were present, so a splash phenomenon was observed. In addition, a splash phenomenon was observed because the material was not fully oxidized and an adequate melt phase was not produced during deposition.
比較例２の蒸着材料は、焼成温度が高いために、材料が過剰に酸化され、蒸着に際して適度な溶融相が生成されなかったため、スプラッシュ現象がわずかに観察された。比較例３及び４の蒸着材料は、焼成温度が高すぎるために、焼成前後の膨張率が３％を越え、材料が過剰に酸化され、蒸着に際して適度な溶融相が生成されなかったため、スプラッシュ現象が観察された。 In the vapor deposition material of Comparative Example 2, since the firing temperature was high, the material was excessively oxidized, and an appropriate melt phase was not generated during the vapor deposition, so a splash phenomenon was slightly observed. Since the vapor deposition materials of Comparative Examples 3 and 4 have a firing temperature that is too high, the expansion coefficient before and after firing exceeds 3%, the material is excessively oxidized, and an appropriate melt phase is not generated during vapor deposition. Was observed.
本発明は、食品や医薬品等の包装材料として有用な、ガスバリア性ケイ素酸化物蒸着層を有する包装材料を製造する際に使用する蒸着材料およびその製造方法として利用できる。 INDUSTRIAL APPLICATION This invention can be utilized as a vapor deposition material used when manufacturing the packaging material which has a gas barrier property silicon oxide vapor deposition layer useful as packaging materials, such as a foodstuff and a pharmaceutical, and its manufacturing method.
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