JPH02299826A - Method of manufacturing transparent gas barrier film - Google Patents
Method of manufacturing transparent gas barrier filmInfo
- Publication number
- JPH02299826A JPH02299826A JP11852489A JP11852489A JPH02299826A JP H02299826 A JPH02299826 A JP H02299826A JP 11852489 A JP11852489 A JP 11852489A JP 11852489 A JP11852489 A JP 11852489A JP H02299826 A JPH02299826 A JP H02299826A
- Authority
- JP
- Japan
- Prior art keywords
- film
- thin film
- silicon oxide
- gas barrier
- heat treatment
- 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.)
- Granted
Links
- 230000004888 barrier function Effects 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 239000010408 film Substances 0.000 claims abstract description 56
- 239000002985 plastic film Substances 0.000 claims abstract description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 26
- 239000010409 thin film Substances 0.000 claims abstract description 26
- 229920003023 plastic Polymers 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 22
- 238000010438 heat treatment Methods 0.000 abstract description 21
- 239000007789 gas Substances 0.000 abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 13
- 239000001301 oxygen Substances 0.000 abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 abstract description 13
- 239000000126 substance Substances 0.000 abstract description 2
- 241001507928 Aria Species 0.000 abstract 1
- 235000004494 Sorbus aria Nutrition 0.000 abstract 1
- 238000000034 method Methods 0.000 description 21
- 229920006255 plastic film Polymers 0.000 description 20
- 239000005022 packaging material Substances 0.000 description 15
- -1 polyethylene Polymers 0.000 description 12
- 230000000704 physical effect Effects 0.000 description 11
- 238000002834 transmittance Methods 0.000 description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229910001882 dioxygen Inorganic materials 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000003447 ipsilateral effect Effects 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 239000005033 polyvinylidene chloride Substances 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000007756 gravure coating Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 208000028659 discharge Diseases 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 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
- 229920001778 nylon Polymers 0.000 description 1
- 229920006284 nylon film Polymers 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、ガスバリヤ性に優れた透明プラスチックフィ
ルムに関するものである。さらに詳しくは、本発明は、
包装材料等としての使用に好適な、ガスバリヤ性に優れ
、しかも透明なプラスチックフィルムに関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a transparent plastic film with excellent gas barrier properties. More specifically, the present invention includes:
The present invention relates to a transparent plastic film that has excellent gas barrier properties and is suitable for use as a packaging material.
食品、医薬品、化学薬品等の包装材料に用いられるプラ
スチックフィルムは、包装された内容物の変質を防ぐた
めに、水蒸気や酸素などのガス透過率の小さい材質のも
のが用いられている。Plastic films used as packaging materials for foods, medicines, chemicals, etc. are made of materials with low permeability to gases such as water vapor and oxygen in order to prevent deterioration of the packaged contents.
例えばこれらのプラスチックフィルムとしては、必要と
される特性に応じて、ポリエチレン、ポリプロピレン、
ポリ塩化ビニリデン等のフィルム、あるいは塩化ビニリ
デンを主成分とし、これと共重合可能な他の化合物、た
とえば塩化ビニル、メチルアクリレート、メチルメタク
リレート、アクリロニトリルなどとの共重合体等の塩化
ビニリデン系樹脂よりなるフィルム、およびこれらの塩
化ビニリデン系樹脂をポリプロピレン、ポリエステル、
ポリアミド等よりなるフィルムにコーティングした塩化
ビニリデン系樹脂コートフィルム等が、ガスバリヤ性を
備えた包装材料として用いられている。For example, these plastic films include polyethylene, polypropylene,
Consisting of vinylidene chloride-based resins such as films of polyvinylidene chloride, etc., or copolymers of vinylidene chloride as a main component and other compounds that can be copolymerized with it, such as vinyl chloride, methyl acrylate, methyl methacrylate, acrylonitrile, etc. film, and these vinylidene chloride resins to polypropylene, polyester,
Vinylidene chloride resin coated films made of polyamide or the like are used as packaging materials with gas barrier properties.
これらのうち、ポリエチレン、ポリプロ、ピレンフィル
ムは、水蒸気バリア性には優れるが、酸素バリア性は低
い、また、ポリ塩化ビニリデン系樹脂フィルムは、ある
程度の水蒸気や酸素に対するガスバリヤ性を備°えては
いるが、それでも必ずしも充分なものではなく、高度な
ガスバリヤ性を必要とする包装材料には不適当であった
。Among these, polyethylene, polypropylene, and pyrene films have excellent water vapor barrier properties but low oxygen barrier properties, and polyvinylidene chloride resin films have gas barrier properties against water vapor and oxygen to some extent. However, even this is not always sufficient and is unsuitable for packaging materials that require high gas barrier properties.
さらにまた、ポリビニルアルコールフィルムや、エチレ
ン−ビニルアルコール共重合体フィルム等のポリビニル
アルコール系フィルムも、酸素バリヤ性に優れているの
で、包装材料として広く用いられている。しかしながら
、ポリビニルアルコール系フィルムは水蒸気バリヤ性に
おいて劣り、さらに高湿度の条件下では酸素バリヤ性も
低下するという欠点を有する。そのためにポリビニルア
ルコール系フィルムを包装材料として用いる場合は、ポ
リプロピレンフィルム、ポリエチレンフィルム、ポリエ
ステルフィルムなどの水蒸気バリヤ性を有するフィルム
を、ポリビニルアルコール系フィルムに積層したフィル
ムが通常用いられている。しかしながら、このような積
層フィルムも、高度なガスバリヤ性を必要とする包装材
料としては、充分にその目的を果たすものとは云えなか
った。Furthermore, polyvinyl alcohol films, such as polyvinyl alcohol films and ethylene-vinyl alcohol copolymer films, have excellent oxygen barrier properties and are therefore widely used as packaging materials. However, polyvinyl alcohol films have the disadvantage that they have poor water vapor barrier properties, and furthermore, their oxygen barrier properties are also reduced under high humidity conditions. For this reason, when a polyvinyl alcohol film is used as a packaging material, a film in which a film having water vapor barrier properties such as a polypropylene film, a polyethylene film, or a polyester film is laminated onto the polyvinyl alcohol film is usually used. However, such laminated films cannot be said to fully fulfill their purpose as packaging materials that require high gas barrier properties.
したがって、このような積層フィルムを高度なガスバリ
ヤ性を必要とする包装材料として使用する場合には、積
層フィルムの厚さを厚くしなければならず、その結果、
積層フィルムの透明性や柔軟性が損なわれてしまい、包
装材料としての好ましい性質が失われてしまう。Therefore, when such a laminated film is used as a packaging material that requires high gas barrier properties, the thickness of the laminated film must be increased, and as a result,
The transparency and flexibility of the laminated film are impaired, and desirable properties as a packaging material are lost.
また、透明ガスバリヤフィルムとしては、二軸延伸ナイ
ロンフィルムや二軸延伸ポリエステルフィルムなどにケ
イ素酸化物を蒸着したフィルムが知られている（例えば
、特公昭５３−１２９５３号公報参照）。Furthermore, as transparent gas barrier films, films in which silicon oxide is vapor-deposited on biaxially stretched nylon films, biaxially stretched polyester films, etc. are known (for example, see Japanese Patent Publication No. 12953/1983).
一般にケイ素酸化物を蒸着したフィルムは、圧力の低い
状態で蒸着を行うとバリヤ性は良好であるが透明性は低
下する。透明性を向上させるためには酸素、水蒸気ガス
を導入し圧力の高い状態で蒸着を行うことが有効である
が、この場合、膜は多孔質となり充分なバリヤ性を得ら
れないという問題があった。In general, films made of silicon oxide have good barrier properties when vapor-deposited under low pressure, but transparency deteriorates. In order to improve transparency, it is effective to introduce oxygen or water vapor gas and perform vapor deposition under high pressure, but in this case, there is a problem that the film becomes porous and sufficient barrier properties cannot be obtained. Ta.
そして、さらに高度のガスバリヤ性が必要な包装材料の
場合には、フィルムにアルミニウム箔を貼り合わせたも
のや、フィルムの表面にアルミニウムを蒸着させたもの
が用いられてきた。しかしながら、このような金属箔等
を用いた包装材料は、水蒸気や酸素などに対するガスバ
リヤ性には優れているものの、不透明であり、内容物を
外から見ることができないという欠点があって、包装材
料としては適当でない面があった。In the case of packaging materials that require even higher gas barrier properties, materials in which aluminum foil is bonded to a film, or materials in which aluminum is vapor-deposited on the surface of the film have been used. However, although packaging materials using such metal foils have excellent gas barrier properties against water vapor and oxygen, they have the disadvantage that they are opaque and the contents cannot be seen from the outside. In some ways, it was not appropriate.
本発明は、前述のような課題を解決し、薄い膜厚でも、
酸素ガスバリヤ性、水蒸気バリヤ性ならびに透明性に優
れ、包装材料として優れた性能を有するフィルムを提供
することを目的とする。The present invention solves the above-mentioned problems, and even with a thin film thickness,
The purpose of the present invention is to provide a film that has excellent oxygen gas barrier properties, water vapor barrier properties, and transparency, and has excellent performance as a packaging material.
すなわち、本発明は、透明プラスチックフィルム基体上
に、ケイ素酸化物の薄膜を設けた後、水分を吸着させ、
次いで熱処理することを特徴とする、透明ガスバリヤフ
ィルムの製造方法を提供するものである。That is, the present invention provides a thin film of silicon oxide on a transparent plastic film substrate, and then adsorbs moisture.
The present invention provides a method for producing a transparent gas barrier film, which is characterized in that the film is then subjected to heat treatment.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明によるどきは、透明プラスチックフィルムを基体
として用いる。基体フィルムとして透明プラスチックフ
ィルムを用いると、最終的に得られるガスバリヤフィル
ムも透明となり、包装材料として使用する際に好適であ
る。According to the present invention, a transparent plastic film is used as the substrate. When a transparent plastic film is used as the base film, the gas barrier film finally obtained will also be transparent, making it suitable for use as a packaging material.
本発明で用いられる透明プラスチックフィルムの例とし
ては、ポリエチレン、ポリプロピレン、ポリブテンなど
のポリオレフィン、ポリエチレンテレフタレート、ポリ
ブチレンテレフタレート、ポリエチレン−２，６−ナフ
タレートなどのポリエステル、ナイロン６、ナイロン１
２などのポリアミド、ポリカーボネート、ポリスチレン
、ポリ塩化ビニル、ポリ塩化ビニリデン、芳香族ポリア
ミド、ポリイミド、ポリビニルアルコール、ポリビニル
ブチラールなどがある。また、これらの共重合体や他の
有機重合体との共重合体であっても良く、他の有機重合
体を含有するものであってら良い、これらの有機重合体
には、公知の添加剤、例えば、帯電防止剤、紫外線吸収
剤、可塑剤、滑剤、着色剤などが添加されていても良い
、これらの透明プラスチックフィルムは強度、伸度、熱
特性、寸法安定性などの点で延伸されていることが好ま
しいが、未延伸であっても良い。Examples of the transparent plastic film used in the present invention include polyolefins such as polyethylene, polypropylene, and polybutene, polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene-2,6-naphthalate, nylon 6, and nylon 1.
2, polyamide, polycarbonate, polystyrene, polyvinyl chloride, polyvinylidene chloride, aromatic polyamide, polyimide, polyvinyl alcohol, polyvinyl butyral, etc. In addition, these copolymers may be copolymers with other organic polymers, or may contain other organic polymers, and known additives may be added to these organic polymers. For example, antistatic agents, ultraviolet absorbers, plasticizers, lubricants, colorants, etc. may be added.These transparent plastic films are stretched in terms of strength, elongation, thermal properties, dimensional stability, etc. Although it is preferable that the film be stretched, it may be unstretched.
透明プラスチックフィルムの光線透過率は、白色光線で
の全光線透過率が少なくとも４０％以上、好ましくは６
０％以上、さらに好ましくは７０％以上、最も好ましく
は８０％以上であることが望ましい０着色剤など公知の
添加剤は、プラスチックフィルムの光線透過率が上の範
囲内になる量で添加されるのが良い。The light transmittance of the transparent plastic film is such that the total light transmittance for white light is at least 40% or more, preferably 6
Known additives such as colorants, which are preferably 0% or more, more preferably 70% or more, and most preferably 80% or more, are added in an amount such that the light transmittance of the plastic film falls within the above range. It's good.
本発明方法によるときは、透明プラスチ・ツクフィルム
上に、ケイ素酸化物の薄膜を形成するに先立ち、コロナ
放電処理、火炎処理、プラズマ処理、グロー放電処理、
粗面化処理などの表面処理や公知のアンカーコート処理
が施されても良く、また他のプラスチックフィルムと積
層されていても良い。When using the method of the present invention, prior to forming a thin film of silicon oxide on a transparent plastic film, corona discharge treatment, flame treatment, plasma treatment, glow discharge treatment,
It may be subjected to surface treatment such as roughening treatment or known anchor coating treatment, or may be laminated with other plastic films.
本発明方法で使用される透明プラスチックフィルムの厚
さは、特に制限を受けるものではないが、３〜４００μ
−の範囲が望ましく、機械強度と可撓性の点でさらに好
ましくは５〜２００μ職の範囲であることが望ましい、
かかる透明プラスチックフィルム基体上にケイ素酸化物
の薄膜が形成される。The thickness of the transparent plastic film used in the method of the present invention is not particularly limited, but is 3 to 400 μm.
- is desirable, and from the point of view of mechanical strength and flexibility, it is more preferably within the range of 5 to 200 μm.
A thin film of silicon oxide is formed on such a transparent plastic film substrate.
本発明方法によるときは、まず、基体の透明プラスチッ
クフィルムの少なくとも片面に、ケイ素酸化物の薄膜を
形成する。この薄膜は、最終的に得られるフィルムに酸
素バリヤ性と水蒸気バリヤ性を付与する機能を果たす、
基体フィルムに薄膜を形成するために使用されるケイ素
酸化物とは、一般式： Ｓ １Ｏｘ（０，５≦Ｘ≦２）
で表されるケイ素の酸化物をいう、このケイ素酸化物に
は、微量の金属や他の金属酸化物、金属水酸化物などを
含んでいても良い。When using the method of the present invention, first, a thin film of silicon oxide is formed on at least one side of a transparent plastic film as a substrate. This thin film functions to provide oxygen barrier properties and water vapor barrier properties to the final film.
The silicon oxide used to form a thin film on the base film has the general formula: S 1Ox (0,5≦X≦2)
This silicon oxide may contain trace amounts of metals, other metal oxides, metal hydroxides, etc.
ケイ素酸化物薄層を形成する方法としては、真空蒸着、
イオンブレーティング、スパッタリングなどを用いる。Methods for forming a silicon oxide thin layer include vacuum evaporation,
Uses ion blating, sputtering, etc.
この際、透明性良好なケイ素酸化物薄膜を形成するため
には、酸素ガス、水蒸気等を導入するのが好ましい。At this time, in order to form a silicon oxide thin film with good transparency, it is preferable to introduce oxygen gas, water vapor, etc.
ケイ素酸化物の薄膜の厚さは、使用するフィルム基体の
厚さと最終的に得られるフィルムの使用目的に合わせて
選定されるが、本発明においては３０人〜５０００人の
範囲が望ましく、好ましくは５０人〜２０００人、さら
に好ましくは１００人〜１０００人が望ましい、３０人
未満ではガスバリヤ性が十分でなく、５０００Å以上で
は基体フィルムが１５μ輪以下のように極めて薄い場合
に、カールが発生するなど平面性を損ない、好ましくな
い。The thickness of the silicon oxide thin film is selected depending on the thickness of the film substrate used and the purpose of use of the final film, but in the present invention, the thickness is preferably in the range of 30 to 5,000. 50 to 2000 people, more preferably 100 to 1000 people. If it is less than 30 people, the gas barrier property will not be sufficient, and if it is more than 5000 Å, curling will occur if the base film is extremely thin, such as 15μ or less. It impairs flatness and is undesirable.
本発明方法では、次に、ケイ素酸化物の薄膜を設けた基
体フィルムに、水分を吸着させる。ケイ素酸化物層に水
分を吸着させる方法としては、ケイ素酸化物、薄膜を形
成したプラスチックフィルムを、高温高湿の環境下、例
えば６０℃−９０％ＲＨの条件で一定期間保管する方式
、水中に一定時間浸漬する方法、薄膜を形成したフィル
ムに水をグラビアコート、リバースコート、スプレーコ
ートあるいは蒸気噴霧等の方法でコーティングする方法
が挙げられるが、これらに限定されるものではない。In the method of the present invention, next, moisture is adsorbed onto the base film provided with a thin film of silicon oxide. Methods for adsorbing moisture to the silicon oxide layer include storing silicon oxide and a plastic film with a thin film for a certain period of time in a high temperature and high humidity environment, e.g. 60°C - 90% RH, or immersing it in water. Examples include, but are not limited to, a method of dipping for a certain period of time, and a method of coating a thin film with water by gravure coating, reverse coating, spray coating, or steam atomization.
本発明方法によるときは、水を吸着させた後の基体フィ
ルムに熱処理を施す、熱処理は、３０〜２００℃の温度
範囲で行うのが好ましいが、これに限定されるものでは
ない、熱処理する温度が３０℃未満では、熱処理に要す
る期間が長くなり、２００℃を越えるとプラスチックフ
ィルム基体が熱収縮をおこし、シワなどが発生しやすく
なるため好ましくない、好ましくは、６０〜１８０℃の
温度範囲で熱処理するのが良い、熱処理方法としては、
熱風乾燥機、恒温恒湿槽などの熱処理装置が適宜使用さ
れる。また熱処理する際の雰囲気の湿度については、特
に制限はない。When using the method of the present invention, the base film after adsorbing water is subjected to heat treatment. The heat treatment is preferably performed at a temperature range of 30 to 200°C, but is not limited to this temperature. If the temperature is less than 30°C, the time required for heat treatment will be longer, and if it exceeds 200°C, the plastic film base will undergo heat shrinkage and wrinkles will easily occur, which is undesirable. It is best to heat treat, the heat treatment method is as follows:
A heat treatment device such as a hot air dryer or a constant temperature and humidity chamber is used as appropriate. Furthermore, there is no particular restriction on the humidity of the atmosphere during heat treatment.
上記熱処理により、ケイ素酸化物の薄膜表面およびケイ
素酸化物の薄膜に形成された微細孔に吸着された水が反
応し、ケイ素酸化物の薄膜に形成された微細孔が塞がれ
る構造となる。そのために酸素および水蒸気が極めて透
過しにくい構造となり、酸素バリヤ性、水蒸気バリヤ性
の優れたものとなる。Through the heat treatment, the water adsorbed on the surface of the silicon oxide thin film and the micropores formed in the silicon oxide thin film reacts, resulting in a structure in which the micropores formed in the silicon oxide thin film are closed. Therefore, the structure becomes extremely impermeable to oxygen and water vapor, resulting in excellent oxygen barrier properties and water vapor barrier properties.
本発明方法による透明ガスバリヤフィルムは、ケイ素酸
化物の薄膜を設けた後に、プラスチックフィルム面およ
び／またはケイ素酸化物薄膜面に、ヒートシール性や耐
摩耗性を与えるためのコーティング、押出しラミネーシ
ョン、あるいは、他のフィルムとの積層や文字、図柄な
どの印刷を適宜行うことができる。The transparent gas barrier film produced by the method of the present invention is produced by coating, extrusion lamination, or extrusion lamination to impart heat sealability and abrasion resistance to the plastic film surface and/or silicon oxide thin film surface after providing the silicon oxide thin film. Lamination with other films and printing of characters, designs, etc. can be performed as appropriate.
本発明方法によって得られる透明ガスバリヤフィルムは
、前述のような方法で製造されるので、プラスチックフ
ィルム基体上に形成された多孔質ケイ素酸化物のａｍ孔
が、水の吸着およびそれに続く熱処理によって、封孔さ
れた構造となり、透明で酸素ガスバリヤ性、水蒸気バリ
ヤ性が共に優れている。このため、包装材料として使用
するときは、内容物の変質を防ぐことができ、かつ内容
物の透視性が良い、よって、食品、医薬品、電気部品、
繊維製品、プラスチック部品などの包装材料として、好
適に用いることができる。Since the transparent gas barrier film obtained by the method of the present invention is produced by the method described above, the AM pores of the porous silicon oxide formed on the plastic film substrate are sealed by water adsorption and subsequent heat treatment. It has a perforated structure, is transparent, and has excellent oxygen gas barrier and water vapor barrier properties. Therefore, when used as a packaging material, it is possible to prevent the contents from deteriorating, and the transparency of the contents is good.
It can be suitably used as a packaging material for textile products, plastic parts, etc.
以下、本発明を実施例にもとづいてさらに詳細に説明す
るが、本発明はその要旨を超えない限り、以下の例に限
定されるものではない。Hereinafter, the present invention will be explained in more detail based on Examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.
なお、実施例における各特性の測定は、次の測定方法に
よったものである。In addition, the measurement of each characteristic in the Examples was based on the following measurement method.
■ 酸素透過度
ＡＳＴＭ Ｄ−３９８５に準じて、酸素透過測定装置（
モタンコントロールス社製、０Ｘ−ＴＲＡＮｌｏｏ ）
を用いて２５℃−８０％ＲＨの条件にて測定した。■ Oxygen permeability measurement device (according to ASTM D-3985)
Manufactured by Motan Controls, 0X-TRANloo)
Measurement was carried out using a 25° C.-80% RH condition.
＠ 透湿度
透湿度測定装置（モダンコントロールズ社製、ト１）を
用いて４０℃−９０％Ｒ）Ｉの条件にて測定した。@ Measurement was performed using a moisture permeability measuring device (Modern Controls Co., Ltd., To1) under the conditions of 40° C.-90% R)I.
■ 光線透過率
分光光度計（日立製作所（株）、自記分光光度計３１０
型）にて、分光透過率を測定し、波長５５０ｎｍでの透
過率を光線透過率とした。■ Light transmittance spectrophotometer (Hitachi, Ltd., self-recording spectrophotometer 310)
The spectral transmittance was measured using a mold), and the transmittance at a wavelength of 550 nm was defined as the light transmittance.
犬ＪＬＩＬｕ
厚さ１２μの二軸延伸ポリエチレンテレフタレー）（Ｐ
ＥＴ）フィルムの表面に、Ｉ Ｘ １０−’Ｔｏｒｒの
真空下、高周波誘導加熱方式で純度９９．９％の一酸化
ケイ素（Ｓ ｉｏ ）を加熱蒸発させ、５００人のケイ
素酸化物の薄膜を形成させた。Dog JLILu 12μ thick biaxially oriented polyethylene terephthalate) (P
ET) Silicon monoxide (Sio) with a purity of 99.9% is heated and evaporated on the surface of the film using a high-frequency induction heating method under a vacuum of I x 10-'Torr to form a thin film of 500 silicon oxides. I let it happen.
次にこのケイ素酸化物の薄膜に水分を吸着させるため、
６０℃−９０％Ｒ）（の雰囲気下に１分間放置した。Next, in order to adsorb moisture to this thin film of silicon oxide,
The sample was left in an atmosphere of 60° C.-90% R) for 1 minute.
この後１５０℃の熱風乾燥機で３分間熱処理を行った。Thereafter, heat treatment was performed for 3 minutes in a hot air dryer at 150°C.
得られたプラスチックフィルムについて、前記の方法で
酸素透過度、透湿度、光線透過率を測定した。測定の結
果を表−１に示す。The obtained plastic film was measured for oxygen permeability, moisture permeability, and light transmittance using the methods described above. The measurement results are shown in Table-1.
え奮且−ユ
実施例１に記載の例において、熱処理条件を１５０℃、
５秒としたほかは、同側におけると同様の手順でプラス
チックフィルムを製造した。得られたフィルムについて
、同様に諸物性を評価した。その結果を表−１に示す。In the example described in Example 1, the heat treatment conditions were set to 150°C;
A plastic film was produced using the same procedure as for the ipsilateral side, except that the time was 5 seconds. The various physical properties of the obtained film were evaluated in the same manner. The results are shown in Table-1.
え１且−ユ
実施例１に記載の例において、水分の吸着方法をグラビ
アコートとし、ケイ素酸化物の薄膜上に水を６９／ａ２
！！！布し、この後１００℃で３０分間熱処理を行った
ほかは、同側におけると同様の手順でプラスチックフィ
ルムを製造した。得られたフィルムについて、同様に諸
物性を評価した。その結果を表−１に示す。In the example described in Example 1, the moisture adsorption method was gravure coating, and water was applied on the silicon oxide thin film at 69/a2.
! ! ! A plastic film was produced in the same manner as on the same side, except that the plastic film was wrapped and then heat treated at 100° C. for 30 minutes. The various physical properties of the obtained film were evaluated in the same manner. The results are shown in Table-1.
良胤透−１
実施例３に記載の例において、熱処理条件を１５０℃で
３分間としたほかは、同側におけると同様の手順でプラ
スチックフィルムを製造した。Ryotane Toru-1 In the example described in Example 3, a plastic film was manufactured in the same manner as on the same side except that the heat treatment conditions were changed to 150° C. for 3 minutes.
得られたフィルムについて、同様に諸物性を評価した。The various physical properties of the obtained film were evaluated in the same manner.
その結果を表−１に示す。The results are shown in Table-1.
１１匠−ｊ
実施例１に記載の例において、水分の吸着方法を水中浸
漬とし、５秒間浸漬後、１５０℃で３分間熱処理を行っ
たほかは、同側におけると同様の手順でプラスチックフ
ィルムを製造した。得られたフィルムについて、同様に
諸物性を評価した。11 Takumi-j In the example described in Example 1, the plastic film was prepared in the same manner as on the same side, except that the moisture adsorption method was immersion in water, and after immersion for 5 seconds, heat treatment was performed at 150°C for 3 minutes. Manufactured. The various physical properties of the obtained film were evaluated in the same manner.
その結果を表−１に示す。The results are shown in Table-1.
え１匠−玉
実施ｒＩＡ２に記載の例において、蒸着時の圧力を４
Ｘ Ｉ Ｏ−’Ｔｏｒｒとしたほかは、同側におけると
同様の手順でプラスチックフィルムを製造した。得られ
たフィルムについて、諸物性を評価した。その結果を表
−１に示す。In the example described in E1 Takumi-Tamajitsu rIA2, the pressure during vapor deposition was set to 4
A plastic film was produced using the same procedure as on the ipsilateral side, except that X I O-'Torr was used. Various physical properties of the obtained film were evaluated. The results are shown in Table-1.
え１皿−１
実施例４に記載の例において、蒸着時の圧力を４ Ｘ
１０−’Ｔｏｒｒに変えたほかは、同側におけると同様
の手順でプラスチックフィルムを製造した。E1 Dish-1 In the example described in Example 4, the pressure during vapor deposition was 4
A plastic film was prepared using the same procedure as on the ipsilateral side, except that the 10-'Torr was changed.
得られたフィルムについて、諸物性を評価した。Various physical properties of the obtained film were evaluated.
その結果を表−１に示す。The results are shown in Table-1.
ル［１
実施例１に記載の例において、蒸着時の圧力をＩ Ｘ
１０ ”５Ｔｏｒｒに変え、水分の吸着および熱処理を
行わなかったほかは、同例におけると同様の手順でプラ
スチックフィルムを製造した。得られたフィルムについ
て、諸物性を評価した。その結果を表−１に示す。[1] In the example described in Example 1, the pressure during vapor deposition is
A plastic film was produced in the same manner as in the same example except that the pressure was changed to 10"5 Torr and no moisture adsorption or heat treatment was performed. Various physical properties of the obtained film were evaluated. The results are shown in Table 1. Shown below.
厖狡侃−１
実施例１に記載の例において、水分の吸着および熱処理
を行わなかったほかは、同例におけると同様の手順でプ
ラスチックフィルムを製造した。EXAMPLE 1 A plastic film was produced in the same manner as in Example 1, except that moisture adsorption and heat treatment were not performed.
得られたフィルムについて、諸物性を評価した。Various physical properties of the obtained film were evaluated.
その結果を表−１に示す。The results are shown in Table-1.
比」［倒−ユ
実施例１に記載の例において、水分の吸着を行わず、熱
処理のみ１５０℃で３分間と変えたほかは、同例におけ
ると同様の手順でプラスチックフィルムを製造した。得
られたフィルムについて、諸物性を評価しな、その結果
を表−１に示す。A plastic film was produced in the same manner as in Example 1, except that no moisture was adsorbed and only the heat treatment was changed to 150° C. for 3 minutes. The obtained film was evaluated for various physical properties, and the results are shown in Table 1.
比１−−−迭
実施例６に記載の例において、水分の吸着および熱処理
を行なわなかったほかは、同例におけると同様の手順で
プラスチックフィルムを得た。得られたフィルムについ
て、諸物性を評価した。その結果を表−１に示す。Ratio 1 --- A plastic film was obtained in the same manner as in Example 6, except that moisture adsorption and heat treatment were not performed. Various physical properties of the obtained film were evaluated. The results are shown in Table-1.
Ｌ靴五−ｊ
実施例１〜７において使用した二軸延伸ＰＥＴフィルム
について、諸物性を評価した。その結果を表−１に示す
。L Shoes 5-j Various physical properties of the biaxially stretched PET films used in Examples 1 to 7 were evaluated. The results are shown in Table-1.
表−１から明らかなように、本発明方法により製造され
たフィルムは、酸素ガスバリヤ性、水蒸気バリヤ性が共
に優れ、透明性も全く損なわれていないことがわかる。As is clear from Table 1, the film produced by the method of the present invention has excellent oxygen gas barrier properties and water vapor barrier properties, and its transparency is not impaired at all.
Claims (1)
膜を設けた後、水分を吸着させ、次いで熱処理すること
を特徴とする、透明ガスバリヤフィルムの製造方法。A method for producing a transparent gas barrier film, which comprises providing a thin film of silicon oxide on a transparent plastic film substrate, adsorbing moisture, and then heat-treating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11852489A JP2674827B2 (en) | 1989-05-15 | 1989-05-15 | Method for producing transparent gas barrier film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11852489A JP2674827B2 (en) | 1989-05-15 | 1989-05-15 | Method for producing transparent gas barrier film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02299826A true JPH02299826A (en) | 1990-12-12 |
| JP2674827B2 JP2674827B2 (en) | 1997-11-12 |
Family
ID=14738743
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11852489A Expired - Lifetime JP2674827B2 (en) | 1989-05-15 | 1989-05-15 | Method for producing transparent gas barrier film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2674827B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05177759A (en) * | 1991-12-28 | 1993-07-20 | Toppan Printing Co Ltd | Laminated packing material |
| US6720097B2 (en) | 2000-10-13 | 2004-04-13 | Dai Nippon Printing Co., Ltd. | Barrier film and method for production thereof |
| EP1688246A4 (en) * | 2003-11-27 | 2008-05-21 | Mitsubishi Plastics Inc | Gas barrier film |
| US7678448B2 (en) | 2004-01-27 | 2010-03-16 | Mitsubishi Plastics, Inc. | Gas barrier film and gas barrier laminate |
| US7910213B2 (en) | 2004-03-25 | 2011-03-22 | Mitsubishi Plastics, Inc. | Gas-barrier laminate |
| US8124236B2 (en) | 2005-07-27 | 2012-02-28 | Mitsubishi Plastics, Inc. | Gas-barrier laminate for hydrothermal treatment |
| US9650191B2 (en) | 2011-03-31 | 2017-05-16 | Mitsubishi Plastics, Inc. | Vapor-deposited film having barrier performance |
-
1989
- 1989-05-15 JP JP11852489A patent/JP2674827B2/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05177759A (en) * | 1991-12-28 | 1993-07-20 | Toppan Printing Co Ltd | Laminated packing material |
| JP2624073B2 (en) * | 1991-12-28 | 1997-06-25 | 凸版印刷株式会社 | Laminated packaging material |
| US6720097B2 (en) | 2000-10-13 | 2004-04-13 | Dai Nippon Printing Co., Ltd. | Barrier film and method for production thereof |
| EP1688246A4 (en) * | 2003-11-27 | 2008-05-21 | Mitsubishi Plastics Inc | Gas barrier film |
| US7678448B2 (en) | 2004-01-27 | 2010-03-16 | Mitsubishi Plastics, Inc. | Gas barrier film and gas barrier laminate |
| US7910213B2 (en) | 2004-03-25 | 2011-03-22 | Mitsubishi Plastics, Inc. | Gas-barrier laminate |
| US8124236B2 (en) | 2005-07-27 | 2012-02-28 | Mitsubishi Plastics, Inc. | Gas-barrier laminate for hydrothermal treatment |
| US9650191B2 (en) | 2011-03-31 | 2017-05-16 | Mitsubishi Plastics, Inc. | Vapor-deposited film having barrier performance |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2674827B2 (en) | 1997-11-12 |
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