JPH01297237A - Vapor deposition film - Google Patents
Vapor deposition filmInfo
- Publication number
- JPH01297237A JPH01297237A JP63127547A JP12754788A JPH01297237A JP H01297237 A JPH01297237 A JP H01297237A JP 63127547 A JP63127547 A JP 63127547A JP 12754788 A JP12754788 A JP 12754788A JP H01297237 A JPH01297237 A JP H01297237A
- Authority
- JP
- Japan
- Prior art keywords
- film
- vapor
- vapor deposition
- deposited
- base material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000007740 vapor deposition Methods 0.000 title abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 23
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims abstract description 9
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229910001634 calcium fluoride Inorganic materials 0.000 claims abstract description 8
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229920006254 polymer film Polymers 0.000 claims abstract description 5
- 239000010408 film Substances 0.000 claims description 52
- 239000010409 thin film Substances 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 230000004888 barrier function Effects 0.000 abstract description 26
- -1 polyethylene Polymers 0.000 abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 15
- 239000001301 oxygen Substances 0.000 abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 abstract description 15
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 9
- 239000000395 magnesium oxide Substances 0.000 abstract description 8
- 238000004544 sputter deposition Methods 0.000 abstract description 8
- 229920005989 resin Polymers 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 7
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 abstract description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 abstract description 5
- 239000004698 Polyethylene Substances 0.000 abstract description 5
- 239000004743 Polypropylene Substances 0.000 abstract description 5
- 239000011777 magnesium Substances 0.000 abstract description 5
- 229920000573 polyethylene Polymers 0.000 abstract description 5
- 229920001155 polypropylene Polymers 0.000 abstract description 5
- 239000000292 calcium oxide Substances 0.000 abstract description 4
- 239000011575 calcium Substances 0.000 abstract description 3
- 239000005020 polyethylene terephthalate Substances 0.000 abstract description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 abstract description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 abstract description 2
- 125000005487 naphthalate group Chemical group 0.000 abstract description 2
- 238000005240 physical vapour deposition Methods 0.000 abstract description 2
- 229920006255 plastic film Polymers 0.000 abstract description 2
- 239000002985 plastic film Substances 0.000 abstract description 2
- 239000012528 membrane Substances 0.000 abstract 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 abstract 2
- 239000000347 magnesium hydroxide Substances 0.000 abstract 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 abstract 2
- 235000012254 magnesium hydroxide Nutrition 0.000 abstract 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 abstract 1
- 239000000920 calcium hydroxide Substances 0.000 abstract 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 abstract 1
- 235000011116 calcium hydroxide Nutrition 0.000 abstract 1
- 238000007733 ion plating Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000005022 packaging material Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000005026 oriented polypropylene Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 229920000298 Cellophane Polymers 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 229920002978 Vinylon Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229920006233 biaxially oriented polyamide Polymers 0.000 description 1
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 1
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 208000028659 discharge Diseases 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000010849 ion bombardment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 239000011104 metalized film Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、高分子フィルムからなる基材に金属フン化物
薄膜を設けた高度に透明性を有する蒸着フィルムに関し
、特にガスバリアー性の優れた蒸着フィルムに関する。[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a highly transparent vapor-deposited film in which a metal fluoride thin film is provided on a base material made of a polymer film, and in particular, a vapor-deposited film with excellent gas barrier properties. Regarding vapor deposited films.
〈従来技術およびその問題点〉
医薬、食品の包装分野において、内容物の保護性を高め
るため、包装に用いる材料には種々の物性が要求され、
これら要求される物性は増々高いものが望まれるように
なってきている。<Prior art and its problems> In the field of pharmaceutical and food packaging, materials used for packaging are required to have various physical properties in order to enhance the protection of contents.
These required physical properties are becoming increasingly desirable.
特に内容物の保護のうち、内容物の変質、酸化防止の点
から、酸素バリアー性、水蒸気バリアー性は、包装材料
には欠くことのできない事項で、今日これらのバリアー
性を付与することは、−S的になりつつあり、その観点
から包装材料の設計が行われている。Oxygen barrier properties and water vapor barrier properties are indispensable for packaging materials, especially from the viewpoint of protecting the contents from deterioration and oxidation. -S, and packaging materials are being designed from this perspective.
一般的に、酸素バリアー性という面からは、エチレンビ
ニルアルコール共重合体、ポリビニルアルコールのホル
マール化合物(ビニロン)、二軸延伸ポリアミド(ON
y ) 、未延伸ポリアミド(CNy)、セロハン等は
優れている。In general, from the perspective of oxygen barrier properties, ethylene vinyl alcohol copolymers, polyvinyl alcohol formal compounds (vinylon), biaxially oriented polyamides (ON
y), unstretched polyamide (CNy), cellophane, etc. are excellent.
また、水蒸気バリアー性という面からは二軸延伸ポリプ
ロピレン(OPP ) 、未延伸ボリリブロビレン(o
pp )等が優れている。In addition, from the perspective of water vapor barrier properties, biaxially oriented polypropylene (OPP) and unoriented polypropylene (o
pp) etc. are excellent.
一方・酸素、水蒸気両バリアー性を備えたものは、ポリ
ビニリデン樹脂、ポリビニリデン−ポリアクリ酸共重合
体樹脂等を各種フィルムにコーティングしたいわゆる、
Kセロハン、KOP 5KPETSKOIJy、Kビニ
ロンがある。On the other hand, those with both oxygen and water vapor barrier properties are so-called films coated with polyvinylidene resin, polyvinylidene-polyacrylic acid copolymer resin, etc.
There are K cellophane, KOP 5KPET SKOIJy, and K vinylon.
しかし、これらは、遮光性、保香性の点でアルミ箔には
劣り、上記側々の材料にそれぞれ長所をもつものの、単
体ではあらゆる物性を持ち備えることができないので、
二種以上の異種材質を積層することで、複合機能を有す
る積層体として用いられる。However, these materials are inferior to aluminum foil in terms of light-shielding and fragrance-retaining properties, and although each of the above materials has its own advantages, it is not possible to have all the physical properties by itself.
By laminating two or more different materials, it can be used as a laminate with multiple functions.
アルミ箔は、水蒸気、酸素バリアー両物性が極めて優れ
ており、光沢性の点ではデイスプレィ効果もあるが、2
0μ以下では耐ピンホール性の点、また、コスト面から
も最近では、PET 、 ONy 、 Opp、 cp
p等の基材にアルミニウム(AL)を真空蒸着した蒸着
フィルムが防湿、酸素バリアー性、遮光性、保香性デイ
スプレィ効果の点で活発に用いられている。Aluminum foil has extremely good water vapor and oxygen barrier properties, and has a display effect in terms of gloss, but
Below 0μ, PET, ONy, Opp, cp are recently used from the point of view of pinhole resistance and cost.
A vapor-deposited film in which aluminum (AL) is vacuum-deposited on a base material such as aluminum is actively used for its moisture-proofing, oxygen barrier, light-shielding, and fragrance-retaining display effects.
しかしながら、このような金属蒸着フィルムは、包装材
料として用いた場合、内容物が確認できない、電子レン
ジで加熱できないという透明性の点また、食品包装等の
レトルト用蒸着フィルムとして用いた場合、基材と蒸着
層との密着性が不十分であった。However, when such a metallized film is used as a packaging material, the contents cannot be confirmed, and it cannot be heated in a microwave oven. The adhesion between the film and the vapor deposited layer was insufficient.
また、AI蒸着層に代わり酸化ケイ素、酸化マグネシウ
ム、酸化アルミニウム薄膜を高分子フィルム等に設ける
ことにより、透明性があり、かつ、防湿性、酸素バリア
ー性を付与した蒸着フィルムも提案されている。(特公
昭53−12953公報、特開昭61−51332公報
、特開昭62−179935公報他)しかしながら、上
記酸化けい素、酸化マグネシウム、酸化アルミニウム等
の蒸着薄膜はいずれも下記欠点を存し、性能的に不十分
のものとなっている。すなわち、酸化ケイ素蒸着膜は、
バリアー評価としては、良好であるが、蒸着自体褐色を
帯びており、透明性が不十分であった。In addition, a vapor-deposited film has been proposed that is transparent and has moisture-proofing and oxygen barrier properties by providing a thin film of silicon oxide, magnesium oxide, or aluminum oxide on a polymer film instead of the AI vapor-deposited layer. (Japanese Patent Publication No. 53-12953, Japanese Patent Application Laid-open No. 61-51332, Japanese Patent Application Laid-open No. 62-179935, etc.) However, the above-mentioned vapor-deposited thin films of silicon oxide, magnesium oxide, aluminum oxide, etc. all have the following drawbacks: The performance is insufficient. In other words, the silicon oxide vapor deposited film is
Although the barrier evaluation was good, the vapor deposition itself was brownish and the transparency was insufficient.
酸化マグネシウム蒸着フィルムについては、蒸着層であ
る酸化マグネシウムが経時まで除々に空気中のCO□と
反応し、炭酸マグネシウム等になり、耐水性がなくなっ
たり、バリアー性が共に低下してしまう。Regarding the magnesium oxide vapor-deposited film, the magnesium oxide that is the vapor-deposited layer gradually reacts with CO□ in the air over time and becomes magnesium carbonate, etc., resulting in loss of water resistance and a decrease in barrier properties.
更に酸化アルニウム蒸着フィルムはバリアー性が不十分
である。Furthermore, aluminum oxide vapor-deposited films have insufficient barrier properties.
また、いずれかの上記蒸着フィルムもカールがひどく、
他の基材とのラミネート、蒸着面に文字絵柄等の印刷を
行うなどの後加工時の作業性がきわめて悪いなどの大き
な問題点があった。In addition, any of the above vapor-deposited films also curled badly.
There were major problems such as extremely poor workability during post-processing such as lamination with other base materials and printing of letters and designs on the vapor-deposited surface.
〈発明が解決しようとする課題〉
本発明の目的は、上記従来の欠点を解決するのであり、
その目的とすることにより、新規な蒸着膜を基材上に設
けることで、得られる蒸着フィルムのカールが全くなく
、かつ酸素バリアー性の優れた透明性の高い蒸着フィル
ムを提供するものである。<Problems to be Solved by the Invention> The purpose of the present invention is to solve the above-mentioned conventional drawbacks.
By providing a novel vapor deposited film on a base material, the objective is to provide a highly transparent vapor deposited film that has no curling and has excellent oxygen barrier properties.
〈課題を解決するための手段〉
本発明は、真空系内で真空蒸着、スパッタリング、イオ
ンブレーティング等のPVD法により高分子フィルムか
らなる基材上の少なくとも片面にフッ化マグネシウム、
フッ化カルシウムの薄膜層を設けた蒸着フィルムである
。<Means for Solving the Problems> The present invention provides magnesium fluoride,
It is a vapor deposited film with a thin layer of calcium fluoride.
以下具体的述べると本発明で用いる基材のプラスチック
フィルムは、ポリニレチン、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、ポリエチレンナフタ
レート、ポリカーボネート、ポリウレタン等のは一種以
上の樹脂から得られる未延伸、任意の延伸倍率、を持つ
フィルム、シートであって、表面平滑性、安定性付与の
ため添加荊を含んでもかまわないが、真空下でそれらが
表面ヘブリードし、基材と薄膜の密着性が低下してしま
う点から、極力低添加物含有の樹脂から成るフィルム、
シート好ましく、特に、透明性、耐熱性のあるポリエチ
レンテレフタート(PET ) 、ポリエチレンナフチ
レート(PEN )等が好ましい。Specifically, the base plastic film used in the present invention is unstretched, obtained from one or more resins such as polynyletine, polypropylene, polyamide, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyurethane, etc., at any stretching ratio, It is a film or sheet that has a thin layer, and may contain additives to provide surface smoothness and stability. , a film made of resin containing as few additives as possible,
Sheets are preferred, and polyethylene terephtate (PET), polyethylene naphthylate (PEN), etc., which are transparent and heat resistant, are particularly preferred.
本発明でいう透明薄膜というのは、真空系内で、抵抗加
熱、高周波融等加熱、電子ビーム加熱方式を用いた一般
的な真空蒸着法、高周波スパッタリング(RF)等のマ
グネトロンスパッタリング、更にはイオンブレーティン
グ等いずれの方法により得られる薄膜であってもかまわ
ない。The transparent thin film referred to in the present invention refers to general vacuum evaporation methods using resistance heating, high frequency fusion heating, electron beam heating method, magnetron sputtering such as radio frequency sputtering (RF), and even ion sputtering in a vacuum system. The thin film may be obtained by any method such as brating.
基材との密着性の点で、イオンブレーティング、スパッ
タリングが優れているが、巻取状で高速加工でき、経済
面で蒸着がもっとも有利である。Ion blating and sputtering are superior in terms of adhesion to the substrate, but vapor deposition is the most advantageous from an economical point of view, as it can be processed at high speed in a rolled form.
また、得られた蒸着フィルムの物性面でも十分満足のい
くものができる。Furthermore, the physical properties of the resulting vapor-deposited film are also sufficiently satisfactory.
上記方法で得られた本発明でいうフッ化マグネシウム、
及びフッ化カルシウム薄膜というのは、それぞれ、Mg
、阿gF、MgFz、MgO,Mg (OH) z、阿
gcOt+Mg(0■) z + 3t(t Or C
a 、CaF + CaF t + CaO+ Ca
(O)I) t )の混合状態と考えられ、それぞれの
含有比等は、’Fii#作製する際、真空系内の真空度
、水蒸気分圧、残留酸素分圧、基盤温度等により異なる
。Magnesium fluoride according to the present invention obtained by the above method,
and calcium fluoride thin film are Mg
, AgF, MgFz, MgO, Mg (OH) z, AgcOt+Mg(0■) z + 3t(t Or C
a, CaF + CaFt + CaO+ Ca
It is considered to be a mixed state of (O)I) t ), and the content ratio of each varies depending on the degree of vacuum in the vacuum system, water vapor partial pressure, residual oxygen partial pressure, substrate temperature, etc. when producing 'Fii#.
本発明でいう透明薄膜というのは、上記薄膜成分が任意
の組成から成っていることを特徴とし、他に、Li、B
e、B、Na+Mg+AI、St、’P、CI、に、T
i、Cr、Mn、Fe。The transparent thin film referred to in the present invention is characterized in that the above-mentioned thin film components are composed of an arbitrary composition, and in addition, Li, B
e,B,Na+Mg+AI,St,'P,CI,ni,T
i, Cr, Mn, Fe.
Co、Ni、Cu、Zn、Pb等の無機質として含有し
ていても10重量%以下で物性面に影響しない範囲であ
ればかまわない。Even if it is contained as an inorganic substance such as Co, Ni, Cu, Zn, Pb, etc., it may be contained in an amount of 10% by weight or less as long as it does not affect the physical properties.
含有両が増加するとイオンエネルギーの小すい金属成分
により蒸着膜の耐水性が低下し、バリアー性の劣化をひ
きおこすので、含有両として5重量%以下であるこが好
ましい。When the content of both metals increases, the water resistance of the deposited film decreases due to metal components with low ionic energy, causing deterioration of barrier properties, so it is preferable that the content of both metals is 5% by weight or less.
また、近紫外部領域の波長吸収を付与するために、薄膜
中のpeff+濃度をコントロールすることで、それに
応じて近紫外部の波長を吸収することもできる。Further, in order to provide wavelength absorption in the near ultraviolet region, by controlling the peff+ concentration in the thin film, it is also possible to absorb wavelengths in the near ultraviolet region accordingly.
薄膜厚としては300Å〜3000人が適当であり、3
00Å以下であると基材上に均一な薄膜が形成されず、
結果として、バリアー性が不十分となる。3000Å以
上になると薄膜に亀裂を生じバリアー性は急激に低下し
てしまう。このようなことにより、500〜1000人
が好ましい。The appropriate thin film thickness is 300 Å to 3000 Å, and 3
If it is less than 00 Å, a uniform thin film will not be formed on the base material,
As a result, barrier properties become insufficient. If the thickness exceeds 3000 Å, cracks will occur in the thin film and the barrier properties will drop sharply. For this reason, 500 to 1000 people is preferable.
また、本発明の蒸着フィルム上にポリエチレン、ポリプ
ロピレン等のヒートシール性を有する樹脂を押出しコー
ティング、あるいは、上記樹脂から成るフィルムをシー
ル層とし、蒸着フィルムと積層複合化するごとで、バリ
アー包材材料として用いる。In addition, by extrusion coating a heat-sealable resin such as polyethylene or polypropylene on the vapor-deposited film of the present invention, or by laminating a film made of the above-mentioned resin as a sealing layer and laminating it with the vapor-deposited film, it is possible to create a barrier packaging material. used as
特に食品等の内容物をレトルト法などにより殺菌処理す
るための、いわゆるレトルト用包装バリアー材料として
用いる場合は蒸着フィルムの外層に文字、絵柄等の印刷
層を設けたポリエチレンテレフタレート、二輪延伸ポリ
プロピレン、二軸延伸ナイロン等の外層フィルムとなり
うるちのをすくなくとも一層設け、かつ該外層フィルム
を外層フィルムを蒸着フィルムの非蒸着側を積層し、最
内層にシーラントとなりうるオレフィンを設けて積層化
した複合フィルムが好ましい。In particular, when used as a so-called retort packaging barrier material for sterilizing the contents of foods and the like by retorting, polyethylene terephthalate, two-wheel oriented polypropylene, two-wheel oriented polypropylene, etc., with a printed layer of letters, designs, etc. on the outer layer of the vapor-deposited film are used. It is preferable to use a composite film in which at least one layer of material that can be used as an outer layer film such as axially oriented nylon is provided, the outer layer film is laminated with the non-deposited side of the vapor-deposited film, and an olefin that can be used as a sealant is provided in the innermost layer. .
レトルト条件下は加温加圧により包材にはかなり熱、ス
トレスが加わり少なくとも最外層はそれにより、多少伸
びが生じ、また急冷により前述したように基材と蒸着界
面に否が生じ、蒸着層の密着性が不十分となり、最悪の
場合は、蒸着層が剥離してしまう。Under retort conditions, the packaging material undergoes considerable heat and stress due to heating and pressurization, causing some elongation at least in the outermost layer.Also, due to rapid cooling, cracks occur at the interface between the base material and the evaporation layer, as described above, and the evaporation layer The adhesion becomes insufficient, and in the worst case, the deposited layer will peel off.
このようなことから、蒸着層は、極力最内層のオレフィ
ン層側に近いところに設けて、積層化することが望まし
い。For this reason, it is desirable that the vapor deposition layer be provided as close as possible to the innermost olefin layer side and laminated.
また、本発明における透明薄膜を形成する手段は先に述
べたようないずれの方法であってもがまわないが、高速
生産性、経済的に考慮すると一般的な抵抗加熱、高周波
誘導、電子ビーム等り加熱手段による真空蒸着が好適で
ある。In addition, the means for forming the transparent thin film in the present invention may be any of the methods mentioned above, but in terms of high-speed productivity and economy, common resistance heating, high-frequency induction, and electron beam methods are suitable. Vacuum deposition using heating means is preferred.
スパッタリング、イオンブレーティング等は、基材上へ
の蒸着膜が優れていることから、密着性を重視する際は
、これらの方法が利用できる。Sputtering, ion blating, etc. can be used to form a vapor deposited film on a base material, so these methods can be used when adhesion is important.
また、基材上に薄膜層を形成する際基材には、特定の処
理必要ないが、Ox+Nz+Ar+lle、Ne等のガ
スにより104〜数Torr下での放電処理、いわゆる
低温プラズマ処理、基材上の帯電物、はこり等を不活性
ガスによりスパッタリングし、表面をクリーングするイ
オンボンバード処理をすることで、より基材と密着性の
ある薄膜層が形成される。In addition, when forming a thin film layer on a substrate, the substrate does not require any specific treatment, but discharge treatment under 104 to several Torr with gases such as Ox + Nz + Ar + lle, Ne, etc., so-called low-temperature plasma treatment, By sputtering charged objects, clumps, etc. with an inert gas and performing ion bombardment treatment to clean the surface, a thin film layer with better adhesion to the base material is formed.
更には、基材上に熱硬化型樹脂層を設けることができる
。Furthermore, a thermosetting resin layer can be provided on the base material.
〈作用〉
本発明は真空系内で蒸着スパッタリング、イオンブレー
ティング等のPVD法により基材上に酸化マグネシウム
、酸化カルシウム等から成る300Å〜3000人の薄
膜層を設けることで、高度に透明性のある酸素バリアー
性の付与された、カールの全くない後加工時での作業性
に優れた蒸着フィルムが得られた。<Function> The present invention provides a highly transparent film by forming a thin film layer of 300 Å to 3000 Å made of magnesium oxide, calcium oxide, etc. on a substrate using a PVD method such as vapor deposition sputtering or ion blating in a vacuum system. A vapor-deposited film with a certain oxygen barrier property, no curling, and excellent workability during post-processing was obtained.
〈実施例−1〉
二輪延伸ポリエステルフィルム12μ(奇人製NSフィ
ルム)を基材として片面に電子ビーム加熱による巻取式
蒸着スパッタリング装置(SPW−020特型、日本真
空技術型)を用いて以下の条件で約500人のフン化マ
グネシウム薄膜を連続的に設け、透明蒸着フィルムを得
た。<Example-1> Using a two-wheeled stretched polyester film 12 μm (NS Film manufactured by Kijin) as a base material, the following was performed on one side using a winding type vapor deposition sputtering device (SPW-020 special model, Japan Vacuum Technology Model) using electron beam heating. About 500 magnesium fluoride thin films were continuously applied under the following conditions to obtain a transparent vapor-deposited film.
〈蒸着条件〉
蒸着材料 MgFz (高純度科学研究所製99%UP
)真空度 3 Xl0−S[Torr]蒸着スピード
24〜25[人/S] (水晶発振式モニターにより
連続測定)
ヒJ−ハ”7 6KV−50mA
クリーングロールの温度は一10°Cで、尚、膜厚測定
は、触針式により測定したところ(Dectak U、
日本真空技術型)フィルムの幅方向に対し500人±2
0%以内であった。<Vapor deposition conditions> Vapor deposition material MgFz (99% UP manufactured by Kojundo Science Institute)
) Vacuum degree 3 The film thickness was measured using a stylus method (Dectak U,
Japan Vacuum Technology Type) 500 people ± 2 in the width direction of the film
It was within 0%.
ここで得られた蒸着フィルムの酸素バリアーの酸素バリ
アー性、水蒸気バリアー性を測定したところそれぞれ5
[cc/ rh、 day、atm ] 22561
1100%+11.35[g/ポ、day]で酸素バリ
アー性が良好であった。When the oxygen barrier properties and water vapor barrier properties of the vapor-deposited film obtained here were measured, they were each 5.
[cc/rh, day, atm] 22561
Oxygen barrier properties were good at 1100%+11.35 [g/day].
また透明性を評価するために、分光光度計700〜40
0nm波長での透過率を測定したところ、全レンジで8
5%以上で550nm波長での透過率は90%であり、
極めて高透明性を有していた。In addition, in order to evaluate transparency, a spectrophotometer 700-40
When we measured the transmittance at 0nm wavelength, it was 8 in all ranges.
At 5% or more, the transmittance at a wavelength of 550 nm is 90%,
It had extremely high transparency.
次にカールの度合をみたところまったくカールは生じて
なく、見た目は未処理基材とまったくかわらなかった。Next, when looking at the degree of curl, there was no curling at all, and the appearance was no different from that of the untreated base material.
更にこの蒸着フィルムの蒸着面に二液硬化型ウレタン系
接着剤を塗工し、未延伸ポリプロピレン60μ(ショー
アロマ−AT、昭和電工製)と以下の条件でラミネート
することで、複合フィルムを得た。Furthermore, a two-component curable urethane adhesive was applied to the vapor deposition surface of this vapor-deposited film, and a composite film was obtained by laminating it with unstretched polypropylene 60μ (Show Aroma-AT, manufactured by Showa Denko) under the following conditions. .
く加工条件〉
・接着剤
AD1050EIADRT−10/NC401=100
/4.5 /22.7 (TNV30%)
・版135μm751 格子 ・ニップ圧力4 kg
/C+ト
ラインスピード20m/win
・乾燥温度 70” −80’−80″C・張力
巻出し 6〜7 kg / cmオーブン
6kg/c11
巻取り 5kg/cn+
・インプレッション圧力 3−5 kg 7cm・ヒ
ートロール温度 75℃
〈実施例−2〉
1着膜厚を1000人±20%にするためにラインスピ
ードを変えた以外は実施例−1と同様にして複合フィル
ムを得た。Processing conditions> ・Adhesive AD1050EIADRT-10/NC401=100
/4.5 /22.7 (TNV30%) ・Plate 135 μm 751 grid ・Nip pressure 4 kg
/C+Trine speed 20m/win ・Drying temperature 70"-80'-80"C ・Tension Unwinding 6-7 kg/cm Oven
6kg/c11 Winding 5kg/cn+ ・Impression pressure 3-5 kg 7cm ・Heat roll temperature 75℃ <Example-2> 1 Implemented except that the line speed was changed to make the deposited film thickness 1000 ± 20% A composite film was obtained in the same manner as in Example-1.
〈実施例−3〉
〈実施例−1〉及び〈実施例−2〉と同様な装置を用い
て、以下の条件で蒸着フィルムを得た。<Example-3> Using the same apparatus as in <Example-1> and <Example-2>, a vapor-deposited film was obtained under the following conditions.
蒸着材料 MgFz/CaFt=1 /1 (重量比
)(高純度科学研究所製)
真空度 2.4 Xl0−’ (Torr)蒸着ス
ピード24〜26[人/S ]・・・(水晶発振式モニ
ターによりMgF2成分をモニター)ビームパワー6K
V−50a+A
クーリングロール温度 −10゛C
尚、蒸着膜厚成分を[!PMAで確認したところ、)’
Ig、Ca共に確認され、それぞれの強度比はほぼ同じ
であった。Vapor deposition material MgFz/CaFt=1/1 (weight ratio) (manufactured by Kojundo Science Institute) Vacuum degree 2.4 monitor MgF2 component) Beam power 6K
V-50a+A Cooling roll temperature -10゛C Note that the deposited film thickness component is [! After checking with PMA,)'
Both Ig and Ca were confirmed, and their intensity ratios were almost the same.
〈実施例4.5〉
実施例−1と同様の条件で膜厚をそれぞれ300人、3
000人にした複合フィルムを得た。<Example 4.5> Under the same conditions as Example-1, the film thickness was changed to 300 and 300, respectively.
A composite film of 1,000 ml was obtained.
以上の実施例および比較例の測定結果を表−1に示す。The measurement results of the above Examples and Comparative Examples are shown in Table 1.
く比較例−1〜3〉
SiO(大阪チタニウム製)、Mg0(高純度化学研究
所製 99.9%以上) 、AIzOs (高純度化
学研突所製)をそれぞれ芸着し、得られた蒸着フィルム
を同様に評価した。Comparative Examples-1 to 3> SiO (manufactured by Osaka Titanium), Mg0 (manufactured by Kojundo Kagaku Kenkyusho, 99.9% or more), and AIzOs (manufactured by Kojundo Kagaku Kenkyusho) were each deposited, and the resulting vapor deposition Films were similarly evaluated.
以上の結果を表−1に示す。The above results are shown in Table-1.
(以壬、#、(:l)
〈効果〉
透明性を有する高分子フィルムからなる基材上に300
Å〜3000人のフッ化マグネシウム、フッ化カルシ
ウムの透明薄膜層を設けることで、従来のPVDC,、
KOP SKP[!Tフィルム以上の酸素バリアー性を
存し、かつ上記フィルムのような褐色を帯びていない、
極めて透明性に優れた蒸着フィルムになり、更に、二次
加工時でのカールによる作業性が極めて悪いという問題
がなく、実用性の高い高透明酸素バリアー性を有する蒸
着フィルムが得られた。(Ichi, #, (:l) <Effect> 300 yen on a substrate made of a transparent polymer film
By providing a transparent thin film layer of magnesium fluoride and calcium fluoride of ~3000 Å, conventional PVDC,
KOP SKP [! It has oxygen barrier properties better than T film and does not have a brown color like the above films.
A vapor-deposited film with extremely excellent transparency was obtained, and furthermore, there was no problem of extremely poor workability due to curling during secondary processing, and a highly practical vapor-deposited film with highly transparent oxygen barrier properties was obtained.
Claims (4)
片面に300Å〜3000Åのフッ化マグネシウム、フ
ッ化カルシウムのいずれか一方または、これらの混合物
から成る薄膜層を形成した高度に透明な蒸着フィルム。(1) A highly transparent vapor-deposited film in which a thin film layer of 300 Å to 3000 Å of either magnesium fluoride, calcium fluoride, or a mixture thereof is formed on at least one side of a substrate made of a transparent polymer film.
化マグネシウム、フッ化カルシウムのいずれか一方また
はこれらの混合物からなる請求項(1)の蒸着フィルム
。(2) The vapor-deposited film according to claim (1), wherein the thin film layer is made of either magnesium fluoride, calcium fluoride, or a mixture thereof to which 10% by weight or less of an inorganic substance is added.
または(2)の蒸着フィルム。(3) Claim (1) in which a sealing layer is laminated on the vapor deposited layer side.
Or the vapor-deposited film of (2).
求項(3)の蒸着フィルム。(4) The vapor-deposited film according to claim (3), wherein an outer layer film is provided on the opposite side of the vapor-deposited layer of the base material.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63127547A JPH01297237A (en) | 1988-05-25 | 1988-05-25 | Vapor deposition film |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63127547A JPH01297237A (en) | 1988-05-25 | 1988-05-25 | Vapor deposition film |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH01297237A true JPH01297237A (en) | 1989-11-30 |
Family
ID=14962707
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP63127547A Pending JPH01297237A (en) | 1988-05-25 | 1988-05-25 | Vapor deposition film |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH01297237A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08269691A (en) * | 1995-03-31 | 1996-10-15 | Toppan Printing Co Ltd | Metal coated film |
US5770301A (en) * | 1995-03-14 | 1998-06-23 | Daicel Chemical Industries, Ltd. | Barrier composite films and a method for producing the same |
US5853862A (en) * | 1995-04-11 | 1998-12-29 | Daicel Chemical Industries, Ltd. | Barrier composite films and method of producing the same |
-
1988
- 1988-05-25 JP JP63127547A patent/JPH01297237A/en active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5770301A (en) * | 1995-03-14 | 1998-06-23 | Daicel Chemical Industries, Ltd. | Barrier composite films and a method for producing the same |
JPH08269691A (en) * | 1995-03-31 | 1996-10-15 | Toppan Printing Co Ltd | Metal coated film |
US5853862A (en) * | 1995-04-11 | 1998-12-29 | Daicel Chemical Industries, Ltd. | Barrier composite films and method of producing the same |
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