JPS6049936A - Manufacture of composite film - Google Patents
Manufacture of composite filmInfo
- Publication number
- JPS6049936A JPS6049936A JP15791583A JP15791583A JPS6049936A JP S6049936 A JPS6049936 A JP S6049936A JP 15791583 A JP15791583 A JP 15791583A JP 15791583 A JP15791583 A JP 15791583A JP S6049936 A JPS6049936 A JP S6049936A
- Authority
- JP
- Japan
- Prior art keywords
- film
- composite film
- glass
- low
- temperature plasma
- 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
- 239000002131 composite material Substances 0.000 title claims description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000010408 film Substances 0.000 claims description 31
- 229920000098 polyolefin Polymers 0.000 claims description 14
- 229920005672 polyolefin resin Polymers 0.000 claims description 8
- 239000005368 silicate glass Substances 0.000 claims description 7
- 239000010409 thin film Substances 0.000 claims description 6
- 238000004544 sputter deposition Methods 0.000 claims description 5
- 238000007740 vapor deposition Methods 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 239000002985 plastic film Substances 0.000 claims description 4
- 229920006255 plastic film Polymers 0.000 claims description 4
- 239000005385 borate glass Substances 0.000 claims description 3
- 239000005365 phosphate glass Substances 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 description 19
- 230000001070 adhesive effect Effects 0.000 description 19
- 238000000034 method Methods 0.000 description 11
- 230000004888 barrier function Effects 0.000 description 10
- 230000035699 permeability Effects 0.000 description 10
- 239000011521 glass Substances 0.000 description 9
- 238000009832 plasma treatment Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- -1 polyethylene terephthalate Polymers 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 229910001882 dioxygen Inorganic materials 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000005033 polyvinylidene chloride Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 208000028659 discharge Diseases 0.000 description 2
- 238000010559 graft polymerization reaction Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001336 alkenes 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000010227 cup method (microbiological evaluation) Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000012994 industrial processing Methods 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 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
- 230000014759 maintenance of location Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920006284 nylon film Polymers 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
- 239000005022 packaging material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 1
Landscapes
- Wrappers (AREA)
- Laminated Bodies (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
本発明は、透明であり、かつ衛生性およびバリヤー性に
優れた複合フィルムの製法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a composite film that is transparent and has excellent hygiene and barrier properties.
従来、各種素材の特性を生かすために異種の素材を複合
して積層体とし２種々の要求物性に応えようとする研究
が盛んに行われている。特に食品包装材については厳し
い要求があり２例えば衛生性、防湿性、気体遮断性、紫
外線遮断性、耐水性、耐薬品性。BACKGROUND ART Conventionally, in order to take advantage of the characteristics of various materials, research has been actively conducted on combining different materials to form a laminate to meet various required physical properties. There are particularly strict requirements for food packaging materials, such as hygiene, moisture proofing, gas barrier properties, UV blocking properties, water resistance, and chemical resistance.
耐油性、耐寒性、耐熱性、熱接着性、透明性、フレーバ
ー保持性２強度、コスト、柔軟性などがあり。It has oil resistance, cold resistance, heat resistance, thermal adhesion, transparency, flavor retention, strength, cost, flexibility, etc.
目的に応じた種々の機能が要求される。Various functions are required depending on the purpose.
これらの積層体を得る方法としては、接着剤を用いる方
法と接着剤を用いずにヒートシールラミネーシコン、エ
クストルージョンラミネーションなどによる方法に大別
される。後者は工業的に有用な方法であるが、素材の組
み合わせに制限があるために前者の方法が主流を占めて
いるのが現状である。Methods for obtaining these laminates are broadly divided into methods using an adhesive and methods using heat seal lamination, extrusion lamination, etc. without using an adhesive. Although the latter method is industrially useful, the former method currently predominates due to restrictions on the combination of materials.
従来１食品包装用積層体には、ポリウレタン系接着剤が
用いられている。ポリウレタン系接着剤は優れた接着性
能を示すが、低分子量化合物の食品への移行の可能性が
あること、接着後熟成期間を必要とすることなどの問題
が残っている。このためポリウレタン系接着剤に変えて
カルボキシル基を含有する変性ポリオレフィン系樹脂が
一部に用いられるようになってきている。この変性ポリ
オレフィン系樹脂は、それ自体が衛生性において問題が
少ないと同時にポリオレフィン系樹脂、アルミニウム箔
などへの接着性が良好であるため有用な材料である。し
かしながら、この変性ポリオレフィン系樹脂は２通常食
品包装用積層体の素材として汎用されているポリエチレ
ンテレフタレート （ＰＥＴ）、ポリ塩化ビニリデン、
ポバール、ナイロン、エチレン／酢酸ビニル共重合体の
加水分解物などに対する接着性が少なく。Conventionally, polyurethane adhesives have been used in food packaging laminates. Although polyurethane adhesives exhibit excellent adhesion performance, there remain problems such as the possibility of migration of low molecular weight compounds into foods and the need for an aging period after adhesion. For this reason, modified polyolefin resins containing carboxyl groups are now being used in place of polyurethane adhesives. This modified polyolefin resin itself is a useful material because it has few hygiene problems and has good adhesion to polyolefin resins, aluminum foil, and the like. However, this modified polyolefin resin is commonly used as a material for food packaging laminates, such as polyethylene terephthalate (PET), polyvinylidene chloride,
Poor adhesion to poval, nylon, ethylene/vinyl acetate copolymer hydrolysates, etc.
やはり素材の組み合わせに制限を受けるという問題があ
った。There was also the problem of being limited in the combination of materials.
本発明者等は、ポリエチレンテレフタレート （ＰＥＴ
）フィルムなどのプラスチックフィルムに低温プラズマ
処理を施すことによって、これらプラスチックフィルム
と変性ポリオレフィン系樹脂（または低温プラズマ処理
を施したポリオレフィンフィルム）とを、ポリウレタン
系接着剤を用いなくとも、熱圧着により実用上十分の接
着強度の＠履体を得ることができるとの知見を得ている
が２食品包装用フィルムとして使用する際に重要視され
る水分、酸素ガスなどの気体透過に対するバリヤー性の
面で十分とはいえず、酸素バリヤー性が要求される用途
に対しては２通常ポリビニルアルコール、エチレン／酢
酸ビニル共重合体の加水分解物などを、また、水分バリ
ヤー性が要求される用途に対しては、ポリ塩化ビニリデ
ンを積層する必要があった。The inventors have discovered that polyethylene terephthalate (PET)
) films and other plastic films, it is possible to bond these plastic films and modified polyolefin resins (or low-temperature plasma-treated polyolefin films) by thermocompression bonding without using polyurethane adhesives. It has been found that it is possible to obtain a shoe body with sufficient adhesive strength. However, for applications that require oxygen barrier properties, use polyvinyl alcohol, hydrolyzate of ethylene/vinyl acetate copolymer, etc., and for applications that require moisture barrier properties. It was necessary to laminate polyvinylidene chloride.
しかし、このような多層の積層シートとすることは、コ
ストの面で不利であり、また、工業的にも加工工程が複
雑化すると同時に選定するバリヤーフィルムの種類によ
っては接着剤を使用しないで積層することができないも
のがほとんどであり２本来の衛生性の改良という目的に
矛盾する。However, creating such a multilayer laminated sheet is disadvantageous in terms of cost, and also complicates the industrial processing process.Depending on the type of barrier film selected, it may be necessary to laminate the sheet without using an adhesive. In most cases, it is impossible to do so, which contradicts the original purpose of improving hygiene.
本発明者等は、上記のような現状に鑑み、透明性。In view of the above-mentioned current situation, the inventors of the present invention sought to improve transparency.
バリヤー性および衛生性に優れた複合フィルムを得るべ
（鋭意研究を重ねた結果１本発明を完成したものである
。すなわち１本発明は、プラスチックフィルム表面に、
ケイ酸塩ガラス、リン酸塩ガラスおよびホウ酸塩ガラス
から選ばれる１種もしくは２種以上の薄膜を蒸着もしく
はスパッタリング法により形成する工程（Ａ）、この薄
膜に低温プラスマ処理する工程（Ｂ）、およびこの処理
面にカルボキシル基を含有するポリオレフィンもしくは
低温プラスマ処理したポリオレフィンフィルムを用い、
熱圧着によりポリオレフィン系樹脂層を形成する工程（
Ｃ）からなる複合フィルムの製法を提供するものであり
。The present invention has been completed as a result of intensive research to obtain a composite film with excellent barrier properties and hygienic properties. Namely, the present invention is to obtain a composite film with excellent barrier properties and hygienic properties.
Step (A) of forming one or more thin films selected from silicate glass, phosphate glass, and borate glass by vapor deposition or sputtering; step (B) of treating this thin film with low-temperature plasma; And using a polyolefin containing carboxyl groups or a polyolefin film treated with low temperature plasma on this treated surface,
The process of forming a polyolefin resin layer by thermocompression bonding (
The present invention provides a method for manufacturing a composite film consisting of C).
上記ガラス薄膜を低温プラズマ処理する工程（Ｂ）によ
って、上記ポリオレフィン系樹脂層が実用上十分の接着
強度をもって形成されるのである。By the step (B) of subjecting the glass thin film to low-temperature plasma treatment, the polyolefin resin layer is formed with adhesive strength sufficient for practical use.
本発明において、プラスチックフィルムとしては。In the present invention, as a plastic film.
ポリエステル、特にＰＥＴ、ナイロン、ポリ塩化ビニリ
デン、ポリ塩化ビニル、ポパール、エチレン／酢酸ビニ
ル共重合体の加水分解物、ポリスチレン。Polyesters, especially PET, nylon, polyvinylidene chloride, polyvinyl chloride, Popal, hydrolysates of ethylene/vinyl acetate copolymers, polystyrene.
ポリカーボネート ポリオレフィン、変性ポリオレフィ
ン、セロファン、アクリル系樹脂などのフィルムがあり
、これらのフィルムは目的によって一軸もしくは二軸延
伸したものを使用することができる。There are films made of polycarbonate polyolefin, modified polyolefin, cellophane, acrylic resin, etc., and these films can be uniaxially or biaxially stretched depending on the purpose.
また、これらのフィルムの表面は未処理であってもよい
が、より接着強度を向上せしめる目的などで。The surface of these films may be untreated, but for the purpose of further improving adhesive strength.
サンドブラスト処理、低温プラズマ処理、コロナ放電処
理、あるいはプライマーの塗布などの物理的もしくは化
学低処理を施したものであってもよい。It may be subjected to a physical or chemical treatment such as sandblasting, low-temperature plasma treatment, corona discharge treatment, or coating with a primer.
本発明において、ケイ酸塩ガラスとはケイ酸塩を主成分
とするもので最も汎用されているガラスである。リン酸
塩ガラスおよびホウ酸塩ガラスとはそれぞれ、リン酸お
よびホウ酸塩を主要成分とするガラスである。これらの
薄膜を蒸着もしくはスパッタリング法により形成する工
程（Ａ）は、自体公知の方法によればよく、それぞれを
単独で、もしくは混合して蒸着もしくはスパッタリング
によって薄層を形成する。この工程（Ａ）は工業的には
、従来のポバール、エチレン／酢酸ビニル共重合体の加
水分解物などを積層してバリヤ一層を形成する方法に比
校して、容易に実施することができるという利点がある
。In the present invention, silicate glass is a glass mainly composed of silicate and is the most commonly used glass. Phosphate glass and borate glass are glasses whose main components are phosphoric acid and borate, respectively. The step (A) of forming these thin films by vapor deposition or sputtering may be performed by a method known per se, and each of them may be used alone or in combination to form a thin layer by vapor deposition or sputtering. This step (A) can be easily carried out industrially compared to the conventional method of laminating poval, hydrolyzate of ethylene/vinyl acetate copolymer, etc. to form a single barrier layer. There is an advantage.
これらの薄層の厚さとしては、２００人で十分なバリヤ
ー性を示し、７００人でハイレトルトに相当するバリヤ
ー性を示す。しかし、６０００人を超えるとフレキシビ
リティに問題を生ずるのでこれ以下の厚さとすることが
好ましい。The thickness of these thin layers shows sufficient barrier properties for 200 people, and barrier properties equivalent to high retort for 700 people. However, if the number of people exceeds 6000, problems will arise in flexibility, so it is preferable that the thickness be less than this.
本発明において、低温プラズマ処理する工程（Ｂ）の処
理条件としては、ｌＸｌ０ 〜Ｉ Ｔｏｒｒのアルゴン
１、窒素、酸素、水素もしくはヘリウム、またはこれら
を含むガス中にて、放電値１００Ｗ以上で、０゜１秒以
上、好ましくは１秒以上の処理時間とする。In the present invention, the processing conditions for the step (B) of low-temperature plasma treatment include argon 1, nitrogen, oxygen, hydrogen, helium, or a gas containing these at lXl0 to I Torr, with a discharge value of 100 W or more, and 0 The processing time is 1 second or more, preferably 1 second or more.
放電値を低（シ、またはより短時間処理にすると接着性
の低下を招く。この低温プラスマ処理する工程（Ｂ）は
、蒸着もしくはスパッタリングの工程（Ａ）に引き続き
連続して行うことが可能であり、工業化におけるメリッ
トが大きい。If the discharge value is low or the treatment is performed for a shorter time, the adhesion will deteriorate.This low-temperature plasma treatment step (B) can be performed continuously after the vapor deposition or sputtering step (A). Yes, it has great advantages in industrialization.
本発明において、変性ポリオレフィンとしては。In the present invention, the modified polyolefin includes:
エチレン３ プロピレン、ブテンなどのオレフィンとア
クリル酸、メタクリル酸、イタコン酸、フマル酸。Ethylene 3 Olefins such as propylene and butene and acrylic acid, methacrylic acid, itaconic acid, and fumaric acid.
マレイン酸、無水マレイン酸などのα、β−不飽和カル
ボン酸もしくはその無水物を共重合もしくはグラフト重
合せしめたもの、ポリオレフィンに上記α。Copolymerization or graft polymerization of α, β-unsaturated carboxylic acids such as maleic acid and maleic anhydride or their anhydrides, and polyolefins with the above α.
β−不飽和カルボン酸などをグラフト重合せしめたもの
、あるいはこれらのものに、さらに金属化合物を配合し
た。一般にアイオノマーと呼ばれるものも使用すること
ができ、これらは単独でもよいが未変性のポリオレフィ
ンと混合して用いることもできる。A material obtained by graft polymerization of β-unsaturated carboxylic acid or the like, or a metal compound further added to these products. What is generally called an ionomer can also be used, and these can be used alone or in combination with an unmodified polyolefin.
接着強度の点からカルボキシル基含有不飽和モノマーと
して０，０１重量％以上、好ましくは０．１〜１０重量
％の範囲とする。From the viewpoint of adhesive strength, the amount of the carboxyl group-containing unsaturated monomer is 0.01% by weight or more, preferably in the range of 0.1 to 10% by weight.
本発明において、加熱加圧して融着する条件としては、
変性ポリオレフィンの軟化温度以上とすることが好まし
く、低密度ポリエチレンを主成分とするものでは約１０
０°Ｃ以上、高密度ポリエチレンを主成分とするもので
は約１３５℃以」二、ポリプロピレンを主成分とするも
のでは約１６０°ｃＢ上とする。In the present invention, the conditions for welding by heating and pressurizing are as follows:
The temperature is preferably higher than the softening temperature of the modified polyolefin, and for those whose main component is low density polyethylene, the temperature is about 10
0°C or higher, approximately 135°C or higher for those whose main component is high-density polyethylene, and approximately 160°C or higher for those whose main component is polypropylene.
本発明方法により得られた複合フィルムは、透明性があ
るという特徴を生かして使用することが好ましいが、場
合によっては包装材料としていわゆる腰”があることを
要求されることがあり、透明性は犠牲になるがさらに紙
もしくは合成＆ＩＥなどをｆｉ！１層して使用すること
もできる。It is preferable to use the composite film obtained by the method of the present invention by taking advantage of its transparency, but in some cases it may be required to have so-called stiffness as a packaging material. Although it is a sacrifice, it is also possible to use fi!1 layer of paper or composite & IE.
以下本発明を実施例および比較例によって、さらに具体
的に説明する。The present invention will be explained in more detail below using Examples and Comparative Examples.
実施例に
軸延伸ＰＥＴフィルム（東しく１１ ｗｈ 、商品名ル
ミラーｐＨ，１２μ）の片面に、アルゴンガス７×１０
−”Ｔｏｒｒ中で、酸化ケイ素７１％、酸化アルミニウ
ム１．０％、酸化カルシウム４．３％、酸化マグネシウ
ム１．０％および残部が酸化ナトリウムおよび酸化カリ
ウムであるケイ酸塩ガラスをスバ、タリングし。In an example, argon gas 7×10
- slicing and taring a silicate glass of 71% silicon oxide, 1.0% aluminum oxide, 4.3% calcium oxide, 1.0% magnesium oxide and the balance sodium oxide and potassium oxide in Torr. .
表１に示すようなそれぞれの厚さのガラス薄層を形成し
た。次にこのガラス薄層上に４００Ｗで６０秒間低温プ
ラズマ処理を施した。この処理面に、変性ポリプロピレ
ン（マレイン酸変性ポリプロピレン。Glass thin layers having respective thicknesses as shown in Table 1 were formed. Next, a low temperature plasma treatment was performed on this glass thin layer at 400 W for 60 seconds. This treated surface is coated with modified polypropylene (maleic acid modified polypropylene).
東洋インキ製造０勅製、商品名ライオセント１０６３−
４）から常法によってフィルム化（６０μ）したものを
。Manufactured by Toyo Ink Manufacturing Co., Ltd., product name: Liocent 1063-
4) was made into a film (60 μm) using a conventional method.
１８０℃、線圧５Ｋｇ／ｃｍにて圧着して複合フィルム
を得た。この複合フィルムの接着強度は１．０ Ｋｇ／
１５ｍｍであり、酸素ガス透過率および透湿度を測定
した結果は表１に示すとおりであった。A composite film was obtained by pressure bonding at 180° C. and a linear pressure of 5 kg/cm. The adhesive strength of this composite film is 1.0 Kg/
15 mm, and the results of measuring oxygen gas permeability and moisture permeability are as shown in Table 1.
また、この複合フィルムを１２１°Ｃ２３０分のレトル
ト試験後の接着強度は８００ｇ／１５ｍｍであり。Furthermore, the adhesive strength of this composite film after a retort test at 121° C. for 230 minutes was 800 g/15 mm.
十分実用に耐えるものであった。It was sufficiently practical.
以下余白
表１
（注１）同圧法にて測定、単位はｍｌ／ｍ・２４時間・
１気圧・２５°Ｃである。Margin Table 1 (Note 1) Measured using the isobaric method, units are ml/m・24 hours・
The temperature is 1 atm and 25°C.
（注２ ） ＪＩＳ Ｚ ０２０８ カップ法により測
定（４゛Ｏｔ、ＲＨ９０％）、単位はｇ／ｒｎ’・２４
時間である。(Note 2) Measured by JIS Z 0208 cup method (4゛Ot, RH90%), unit is g/rn'・24
It's time.
（注３）ＮＤは検知されないことを示す。(Note 3) ND indicates not detected.
比較例１
実施例１において、低温プラズマ処理を省略して得た複
合フィルムはほとんど接着強度がなく、容易に引き剥が
された。Comparative Example 1 In Example 1, the composite film obtained by omitting the low-temperature plasma treatment had almost no adhesive strength and was easily peeled off.
実施例２
実施例１においてＰＥＴフィルムに代えてナイロンフィ
ルム（ユニチカ（Ｉｔｌ製、商品名エンブレム、１５μ
）を用い、ケイ酸塩ガラス（酸化ケイ素７４％。Example 2 In Example 1, a nylon film (Unitika (manufactured by Itl, trade name emblem, 15 μm) was used instead of PET film.
) using silicate glass (74% silicon oxide).
酸化カルシウム１０％および酸化ナトリウム１６％）の
の厚さを約５００人とした以外は同様にして得た複合フ
ィルムの接着強度は’、０Ｋｇ７１５ ｍｍ、酸素ガス
透過率は０．０２ ｍｌ／ ｍ・２４時間・１気圧・２
５°Ｃ２透湿度は０．０５ｇ／ｎ？・２４時間であった
。A composite film obtained in the same manner except that the thickness of the composite film (10% calcium oxide and 16% sodium oxide) was changed to about 500 mm, had an adhesive strength of 0 kg, 715 mm, and an oxygen gas permeability of 0.02 ml/m. 24 hours/1 atm/2
5°C2 moisture permeability is 0.05g/n?・It was 24 hours.
実施例３
実施例１において変性ポリオレフィンフィルムに代えて
、５００Ｗ、６０秒の低温プラズマ処理を施したポリエ
チレンフィルム（タマボリ（４１製ＤＴ−２゜商品名、
７０μ）を用い、ケイ酸塩カラスの厚さを２００人とし
た以外は同様にして得た複合フィルムの接着強度は６０
０ ｇ／ １５ｍｍ、酸素カス透過率は１．０ｍｌ／ｎ
（・２４時間・１気圧・２５°Ｃ１透湿度は０．１ｇ／
ｒｄ・２４時間であった。Example 3 In place of the modified polyolefin film in Example 1, a polyethylene film (Tamabori (DT-2° manufactured by 41, trade name,
The adhesive strength of a composite film obtained in the same manner except that the thickness of the silicate glass was 200 μm) was 60 μm.
0 g/15mm, oxygen sludge permeability is 1.0ml/n
(・24 hours・1atm・25°C1 Moisture permeability is 0.1g/
rd・24 hours.
実施例４
実施例２における変性ポリオレフィンフィルムに代えて
、５００Ｗ、６０秒の低温プラズマ処理を施したポリエ
チレンフィルム（実施例３と同じ）を用い、ケイ酸塩ガ
ラスの厚さを５００人とした以外は同様にして得た複合
フィルムの接着強度は６００ｇ／ １５ ｍｍ、酸素ガ
ス透過率は０．２５ ｍｌ／ ｒｒｒ・２４時間・１気
圧・２５℃、透湿度はＯ，Ｏ’１ｇ／ｒｒＦ・２４時間
であった。Example 4 Instead of the modified polyolefin film in Example 2, a polyethylene film (same as Example 3) that had been subjected to low-temperature plasma treatment at 500 W for 60 seconds was used, except that the thickness of the silicate glass was 500 mm. The adhesive strength of the composite film obtained in the same manner was 600 g/15 mm, the oxygen gas permeability was 0.25 ml/rrr, 24 hours, 1 atm, 25°C, and the moisture permeability was O, O'1 g/rrF, 24 It was time.
実施例５〜８
二軸延伸ＰＥＴフィルム（実施例１と同じ）の片面に、
アルゴンと酸素ガス７ Ｘ １０ Ｔｏｒｒ中で表２に
示す組成のガラスを厚さ１０００人にスパッタリングし
、それぞれガラス薄層を形成した。次にこのガラス薄層
上に５００Ｗで６０秒間低温プラズマ処理を施した。Examples 5 to 8 On one side of a biaxially stretched PET film (same as Example 1),
Glass having the composition shown in Table 2 was sputtered to a thickness of 1000 mm in argon and oxygen gas at 7 x 10 Torr to form respective thin glass layers. Next, a low temperature plasma treatment was performed on this glass thin layer at 500 W for 60 seconds.
この処理面に、実施例１と同様に変性ポリオレフィンフ
ィルムを圧着して複合フィルムを得た。これらの複合フ
ィルムの接着強度（Ｋｇ／ １５ ｍｍ） 、酸素ガス
透過率（ｍｌ／ ｎ？ ・２４時間・１気圧・２５°Ｃ
）および透湿度（ｇ／ｎ？・２４時間）を表２に示す。A modified polyolefin film was pressed onto this treated surface in the same manner as in Example 1 to obtain a composite film. Adhesive strength (Kg/15 mm), oxygen gas permeability (ml/n?, 24 hours, 1 atm, 25°C) of these composite films
) and moisture permeability (g/n?・24 hours) are shown in Table 2.
また、これらの複合フィルムを１２１℃、３０分のレト
ルト試験後の接着強度の劣化は全く認められなかった。Furthermore, no deterioration in adhesive strength was observed after these composite films were subjected to a retort test at 121° C. for 30 minutes.
以下余白 表２Below margin Table 2
Claims (1)
もしくは２種以上の薄膜を蒸着もしくはスパッタリング
法により形成する工程（Ａ）、この薄膜を低温プラズマ
処理する工程（Ｂ）、およびこの処理面にカルボキシル
基を含有するポリオレフィンもしくは低温プラズマ処理
したポリオレフィンフィルムを用い、熱圧着によりポリ
オレフィン系樹脂層を形成する工程（Ｃ）からなる複合
フィルムの製法。[Claims] 1. Silicate glass on the surface of the plastic film. A step (A) of forming one or more thin films selected from phosphate glass and borate glass by vapor deposition or sputtering, a step (B) of treating this thin film with low-temperature plasma, and A method for producing a composite film comprising a step (C) of forming a polyolefin resin layer by thermocompression bonding using a polyolefin containing a carboxyl group or a polyolefin film treated with low-temperature plasma.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15791583A JPS6049936A (en) | 1983-08-31 | 1983-08-31 | Manufacture of composite film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15791583A JPS6049936A (en) | 1983-08-31 | 1983-08-31 | Manufacture of composite film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6049936A true JPS6049936A (en) | 1985-03-19 |
| JPH036904B2 JPH036904B2 (en) | 1991-01-31 |
Family
ID=15660233
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15791583A Granted JPS6049936A (en) | 1983-08-31 | 1983-08-31 | Manufacture of composite film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6049936A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6151332A (en) * | 1984-08-20 | 1986-03-13 | 積水化学工業株式会社 | Transparent synthetic resin body having permeability resistance |
| JPS6223744A (en) * | 1985-07-24 | 1987-01-31 | ダイセル化学工業株式会社 | Polyester vessel having excellent gas barriering property |
| JPS6223745A (en) * | 1985-07-24 | 1987-01-31 | ダイセル化学工業株式会社 | Film for gas shielding packaging |
| JPS6225040A (en) * | 1985-07-26 | 1987-02-03 | ダイセル化学工業株式会社 | Plastic molded shape with glass protective film |
| WO2007023708A1 (en) * | 2005-08-25 | 2007-03-01 | Asahi Glass Company, Limited | Base with film and glass for film formation |
| JP2009194039A (en) * | 2008-02-12 | 2009-08-27 | Rohm Co Ltd | Flexible substrate and its manufacturing method |
-
1983
- 1983-08-31 JP JP15791583A patent/JPS6049936A/en active Granted
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6151332A (en) * | 1984-08-20 | 1986-03-13 | 積水化学工業株式会社 | Transparent synthetic resin body having permeability resistance |
| JPH0432147B2 (en) * | 1984-08-20 | 1992-05-28 | ||
| JPS6223744A (en) * | 1985-07-24 | 1987-01-31 | ダイセル化学工業株式会社 | Polyester vessel having excellent gas barriering property |
| JPS6223745A (en) * | 1985-07-24 | 1987-01-31 | ダイセル化学工業株式会社 | Film for gas shielding packaging |
| JPH0531468B2 (en) * | 1985-07-24 | 1993-05-12 | Daicel Chem | |
| JPS6225040A (en) * | 1985-07-26 | 1987-02-03 | ダイセル化学工業株式会社 | Plastic molded shape with glass protective film |
| WO2007023708A1 (en) * | 2005-08-25 | 2007-03-01 | Asahi Glass Company, Limited | Base with film and glass for film formation |
| JPWO2007023708A1 (en) * | 2005-08-25 | 2009-02-26 | 旭硝子株式会社 | Substrate with film and glass for film formation |
| US7923115B2 (en) | 2005-08-25 | 2011-04-12 | Asahi Glass Company, Limited | Substrate with film and glass for formation film |
| JP5136054B2 (en) * | 2005-08-25 | 2013-02-06 | 旭硝子株式会社 | Substrate with film and glass for film formation |
| KR101296415B1 (en) * | 2005-08-25 | 2013-08-13 | 아사히 가라스 가부시키가이샤 | Base with film and glass for film formation |
| JP2009194039A (en) * | 2008-02-12 | 2009-08-27 | Rohm Co Ltd | Flexible substrate and its manufacturing method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH036904B2 (en) | 1991-01-31 |
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