JPH04270650A - Gas barrier-type film - Google Patents
Gas barrier-type filmInfo
- Publication number
- JPH04270650A JPH04270650A JP5608591A JP5608591A JPH04270650A JP H04270650 A JPH04270650 A JP H04270650A JP 5608591 A JP5608591 A JP 5608591A JP 5608591 A JP5608591 A JP 5608591A JP H04270650 A JPH04270650 A JP H04270650A
- Authority
- JP
- Japan
- Prior art keywords
- film
- gas barrier
- kaolinite
- barrier properties
- laminated film
- 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
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052622 kaolinite Inorganic materials 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 229920005989 resin Polymers 0.000 claims abstract description 17
- 239000011347 resin Substances 0.000 claims abstract description 17
- 230000004888 barrier function Effects 0.000 claims description 37
- 229920005992 thermoplastic resin Polymers 0.000 claims description 5
- 108010025435 Permacol Proteins 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 239000007789 gas Substances 0.000 abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 239000000088 plastic resin Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 31
- 238000000576 coating method Methods 0.000 description 17
- -1 polyethylene Polymers 0.000 description 17
- 239000004372 Polyvinyl alcohol Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 229920002451 polyvinyl alcohol Polymers 0.000 description 14
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 13
- 229910001882 dioxygen Inorganic materials 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 9
- 239000005033 polyvinylidene chloride Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000004952 Polyamide Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 229920002647 polyamide Polymers 0.000 description 5
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 239000005022 packaging material Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229920006026 co-polymeric resin Polymers 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 239000002985 plastic film Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000005026 oriented polypropylene Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 238000009455 aseptic packaging Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910001649 dickite Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 229920006284 nylon film Polymers 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920001652 poly(etherketoneketone) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920006350 polyacrylonitrile resin Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001601 polyetherimide 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
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Wrappers (AREA)
- Laminated Bodies (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は酸素、窒素や炭酸ガスな
どの気体の遮断性および透明性に優れた包装材料として
好適な被覆プラスチックフイルムに関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coated plastic film which is suitable as a packaging material and has excellent barrier properties against gases such as oxygen, nitrogen and carbon dioxide, and excellent transparency.
【０００２】従来より、ポリオレフィン、ポリスチレン
、ポリ塩化ビニル、ポリエステル、ポリアミドなどの熱
可塑性樹脂よりなるフイルム、特に配向されたポリプロ
ピレン、ポリエステル、ポリアミド等のフイルムは、優
れた力学的性質や、耐熱性、透明性などを有し広く包装
材料として用いられている。しかし、これらフイルムを
食品包装用として用いる場合には、その気体透過性が大
きすぎることから酸素遮断性が不十分であり、酸化劣化
による場合や好気性微生物による場合など内容物の変質
を招き易く、通常は他の酸素遮断性の良い膜層を積層す
るなどの方法がとられる場合が多い。その最も代表的な
手段としてはアルミニウムなどの金属箔をラミネートし
たり、それ等金属を該熱可塑性樹脂フイルム表面に蒸着
する方法が用いられ、優れた気体遮断性、特に酸素遮断
性が有効に活用されている。[0002] Conventionally, films made of thermoplastic resins such as polyolefin, polystyrene, polyvinyl chloride, polyester, and polyamide, particularly films made of oriented polypropylene, polyester, and polyamide, have excellent mechanical properties, heat resistance, It has transparency and is widely used as a packaging material. However, when these films are used for food packaging, their gas permeability is too high, so their oxygen barrier properties are insufficient, and the contents are susceptible to deterioration due to oxidative deterioration or aerobic microorganisms. , usually a method such as laminating other film layers with good oxygen barrier properties is often used. The most typical method is to laminate a metal foil such as aluminum or to vapor-deposit such a metal on the surface of the thermoplastic resin film, which makes effective use of its excellent gas barrier properties, especially oxygen barrier properties. has been done.
【０００３】しかし、これらのアルミニウムラミネート
や蒸着されたフイルムは不透明となり、これらを用いて
食品の包装を行った場合にその内容物を見ることができ
ないという欠点があり、近年の包装形態の多様化、ファ
ッション化傾向とも相まって透明で気体遮断性に優れた
フイルムへの要求がますます高まっている。一方、従来
より気体透過性の小さな透明プラスチックフイルム素材
も種々知られており、例えばポリビニルアルコールやポ
リエチレンビニルアルコール、およびポリ塩化ビニリデ
ン系樹脂から成るフイルムなどがある。しかし、これら
のフイルムは何れも単独では強度、伸度、耐水性、耐熱
性などの物性が、配向されたポリプロピレン、ポリエス
テル、ポリアミドなどのフイルムに比し不十分であり、
特にポリビニルアルコール、ポリエチレンビニルアルコ
ールなどは非常に吸湿性が大きく、ロール状フイルムの
端面が吸湿によって花びら状になるなど取り扱い性が困
難なものであるとともに、目的である気体遮断性も吸湿
によって大幅に低下してしまう。[0003] However, these aluminum laminates and vapor-deposited films are opaque and have the disadvantage that the contents cannot be seen when food is packaged using them. Coupled with the trend toward fashion, the demand for transparent films with excellent gas barrier properties is increasing. On the other hand, various transparent plastic film materials with low gas permeability have been known, such as films made of polyvinyl alcohol, polyethylene vinyl alcohol, and polyvinylidene chloride resins. However, when used alone, these films have insufficient physical properties such as strength, elongation, water resistance, and heat resistance compared to oriented films such as polypropylene, polyester, and polyamide.
In particular, polyvinyl alcohol, polyethylene vinyl alcohol, etc. are highly hygroscopic, making it difficult to handle as the end surfaces of the rolled film become petal-like due to moisture absorption, and the gas barrier properties, which are the objective, are significantly reduced due to moisture absorption. It will drop.
【０００４】よって、これらのフイルムは包装材料用フ
イルムとして到底単独で用い得るものではなく、通常１
０〜４０μｍ程度のこれらのフイルムを前記ポリプロピ
レンフイルムやポリエステルフイルムなどと共に積層す
ることによって用いられているのが現状である。しかも
これらのフイルムは単独でも何れも高価格であり、複層
化することによって更に高価格なものとなるばかりでな
くトータルの層厚みも非常に厚いものになり、高度の透
明性が得られ難いなどの問題点がある。また、これらの
フイルムによって得られる気体遮断性のレベルも先のア
ルミニウム積層されたフイルムに比べると未だ充分とは
言えないことから、高透明で高度の気体遮断性を有し、
単体で用い得る低価格のフイルムが強く求められている
のが実情である。[0004] Therefore, these films cannot be used alone as packaging material films;
Currently, these films with a thickness of about 0 to 40 μm are laminated together with the polypropylene film, polyester film, etc., and used. Moreover, these films are expensive even when used alone, and when multi-layered, not only do they become even more expensive, but the total layer thickness also becomes extremely thick, making it difficult to obtain a high degree of transparency. There are other problems. In addition, the level of gas barrier properties obtained by these films is still not sufficient compared to the previous aluminum laminated film, so we developed a new film with high transparency and high gas barrier properties.
The reality is that there is a strong demand for low-cost films that can be used alone.
【０００５】一方これらの問題を解決すべく、配向され
たポリプロピレンやポリエステル、ポリアミドなどに前
記ポリビニルアルコール、ポリエチレンビニルアルコー
ル、ポリ塩化ビニリデンなどのバリアー性樹脂を塗布す
る方法も検討されている。しかし、ポリビニルアルコー
ル、ポリエチレンビニルアルコールに就いては、低環境
湿度下では、気体遮断性が優れているが、高環境湿度下
では、その吸湿性より気体遮断性が大幅に低下する問題
点がある。また、ポリ塩化ビニリデンに就いては、その
気体遮断性は環境湿度に依存しないが、十分であるとは
いえず、塗布厚みを大きくすることによって用いられて
いるのが現状である。それでも、その気体遮断性のレベ
ルは、未だ不十分であり、アルミニウム蒸着などのレベ
ルには、程遠いものにすぎない。On the other hand, in order to solve these problems, a method of coating oriented polypropylene, polyester, polyamide, etc. with a barrier resin such as polyvinyl alcohol, polyethylene vinyl alcohol, polyvinylidene chloride, etc. is also being considered. However, although polyvinyl alcohol and polyethylene vinyl alcohol have excellent gas barrier properties under low environmental humidity, they have the problem that their gas barrier properties are significantly lower than their hygroscopic properties under high environmental humidity. . Furthermore, although the gas barrier property of polyvinylidene chloride does not depend on environmental humidity, it cannot be said to be sufficient and is currently used by increasing the coating thickness. However, its level of gas barrier properties is still insufficient and is only far from the level of aluminum vapor deposition.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、上記従来の
課題を解決しようとするものであり、その目的とすると
ころは湿度の影響をうけにくい高度の気体遮断性と高度
の透明性を同時に満足し、かつラミネートなどの多層化
不要で取り扱い性、経済性に優れたプラスチックフイル
ムを提供しようとするものである。[Problems to be Solved by the Invention] The present invention attempts to solve the above-mentioned conventional problems, and its purpose is to simultaneously provide a high degree of gas barrier property and a high degree of transparency that are not easily affected by humidity. The objective is to provide a plastic film that is satisfactory, does not require multi-layering such as lamination, and is excellent in handling and economy.
【０００７】[0007]
【課題を解決するための手段】即ち、本発明のガスバリ
アー性フイルムは、熱可塑性樹脂よりなる基体フイルム
の少くとも片面に、数１で定義されるパーマコール値（
π）が７５ｃａｌ／ｃｃ以上である皮膜形成性を有する
樹脂（Ａ）とカオリナイト（Ｂ）とよりなる組成物とか
らなり、（Ｂ）／（Ａ）の重量比が１／９９〜９０／１
０であるごとく配合された組成物よりなる層が形成され
てなるガスバリアー性フイルムである。[Means for Solving the Problems] That is, the gas barrier film of the present invention has a permacol value (
A composition consisting of a resin (A) having film-forming properties with π) of 75 cal/cc or more and kaolinite (B), the weight ratio of (B)/(A) being 1/99 to 90/ 1
This is a gas barrier film in which a layer is formed of a composition blended so that
【０００８】本発明のガスバリアー性フイルムに用いら
れる基材フイルムとしては、透明なフイルム形成能を有
する熱可塑性樹脂であれば、特に制限はないが、ポリエ
チレン、ポリプロピレンなどのポリオレフィン系樹脂、
ポリエチレンテレフタレート、ポリエチレンイソフタレ
ート、ポリエチレン２，６−ナフタレート、ポリブチレ
ンテレフタレートやそれ等の共重合体などに代表される
ごときポリエステル系樹脂、ポリオキシメチレンに代表
されるごときポリエーテル系樹脂、ナイロン−６、ナイ
ロン−６６、ポリメタキシリレンアジパミドなどに代表
されるごときポリアミド系樹脂、ポリスチレン、ポリ（
メタ）アクリル酸エステル、ポリアクリロニトリル、ポ
リ酢酸ビニルやそれ等の共重合体に代表されるごときビ
ニル系樹脂、ポリカーボネート系樹脂などやセロファン
、アセテートなどに代表されるごときセルロース系樹脂
、更にはポリイミド、ポリエーテルイミド、ポリフェニ
レンスルフィド、ポリエーテルスルフォン、ポリスルフ
ォン、ポリエーテルケトン、ポリエーテルケトンケトン
、フッソ含有重合体、その他の多くの樹脂の単体、共重
合体、混合体、積層体よりなる、未延伸あるいは一軸ま
たは直行する二軸方向に延伸された配向フイルムなどを
挙げることが出来る。なかでも本発明の主旨からは、基
材フイルムには耐熱寸法変化や機械的強度、更には成型
性や経済性などの面から二軸延伸されたポリプロピレン
、ポリエステル、ポリアミドなどのフイルムである場合
が好適である。The base film used in the gas barrier film of the present invention is not particularly limited as long as it is a thermoplastic resin that has the ability to form a transparent film, but polyolefin resins such as polyethylene and polypropylene,
Polyester resins such as polyethylene terephthalate, polyethylene isophthalate, polyethylene 2,6-naphthalate, polybutylene terephthalate and copolymers thereof, polyether resins such as polyoxymethylene, nylon-6 , nylon-66, polyamide resins such as polymethaxylylene adipamide, polystyrene, poly(
Vinyl resins such as meth)acrylic acid esters, polyacrylonitrile, polyvinyl acetate and their copolymers, polycarbonate resins, cellulose resins such as cellophane and acetate, and polyimides, Unstretched products made of simple substances, copolymers, mixtures, and laminates of polyetherimide, polyphenylene sulfide, polyethersulfone, polysulfone, polyetherketone, polyetherketoneketone, fluorine-containing polymers, and many other resins. Alternatively, an oriented film stretched in one axis or two orthogonal directions can be used. In particular, from the perspective of the present invention, the base film may be a biaxially stretched film of polypropylene, polyester, polyamide, etc. from the viewpoint of heat resistance to dimensional change, mechanical strength, moldability, and economical efficiency. suitable.
【０００９】フイルムの厚みは特に限定はされないが、
通常は１〜２５０μｍであり、包装材料としては３〜５
０μｍである場合が特に好ましい。この基材フイルムは
、単体であっても複合された多層フイルムであってもよ
く、多層フイルムにおける複合方法や層数などは任意で
ある。[0009] Although the thickness of the film is not particularly limited,
Normally it is 1 to 250 μm, and as a packaging material it is 3 to 5 μm.
Particularly preferred is 0 μm. This base film may be a single film or a composite multilayer film, and the combination method and number of layers in the multilayer film are arbitrary.
【００１０】本発明は、かかる熱可塑性樹脂フイルムの
少くとも片面に特定の組成物層を積層してなることを本
質とする。表面に積層されるべき配合組成物に用いられ
るカオリナイト（Ｂ）は、カオリンとも呼ばれるもので
、例えば共立出版社刊行の「化学大辞典」に記載されて
いるようなアルミノシリケートからなるものを意味する
。基本化学式はＡｌ２ Ｓｉ２ Ｏ５ （ＯＨ）４ で
、形態は六角板状、不整六角形が一般であるが、たとえ
ば球状のような特殊品でもかまわない。また細管状のハ
ロサイト系でもかまわない。該カオリナイト（Ｂ）は、
天然品であっても合成品でもよい。また、焼成処理品で
もかまわない。該カオリナイト（Ｂ）の粒径は、電子顕
微鏡で測定される平均粒径が２μｍ以下のものが好まし
い。平均粒径が２μｍを越えると気体遮断性を向上させ
る効果が低下し、かつ、透明性が低下するので好ましく
ない。The essence of the present invention is that a layer of a specific composition is laminated on at least one side of such a thermoplastic resin film. Kaolinite (B) used in the compounded composition to be laminated on the surface is also called kaolin, and refers to an aluminosilicate as described in, for example, "Chemistry Dictionary" published by Kyoritsu Shuppansha. do. The basic chemical formula is Al2 Si2 O5 (OH)4, and the shape is generally hexagonal plate-like or irregular hexagonal, but special products such as spherical shapes may also be used. Further, a tubular hallosite type may also be used. The kaolinite (B) is
It may be a natural product or a synthetic product. Further, a fired product may also be used. The particle size of the kaolinite (B) is preferably one in which the average particle size measured with an electron microscope is 2 μm or less. If the average particle size exceeds 2 μm, the effect of improving gas barrier properties will be reduced, and transparency will also be reduced, which is not preferable.
【００１１】該カオリナイト（Ｂ）は、積層された層内
での分散性が良好であることが極めて重要である。この
分散性を向上させるための手段は特に限定はされないが
、たとえば、脱イオン法により精製したカオリナイトを
使用したり、分散性を向上させるための表面処理を施し
たカオリナイトを用いることが有効である。また、この
分散性を向上させるために粉体としてそのまま用いるよ
り、ゾルとして分散処理をして用いる方が好ましい。
該ゾル化の手段も限定はなく、各種の分散手段が任意に
利用できる。また、該ゾル化の時に界面活性剤や高分子
分散剤等の分散助剤を併用することも制限を受けない。It is extremely important that the kaolinite (B) has good dispersibility within the laminated layers. There are no particular limitations on the means to improve this dispersibility, but for example, it is effective to use kaolinite purified by a deionization method, or to use kaolinite that has been surface-treated to improve dispersibility. It is. Furthermore, in order to improve the dispersibility, it is preferable to use the material after dispersion treatment as a sol rather than using it directly as a powder. There is no limitation on the means for making the sol, and various dispersion means can be used as desired. Furthermore, there is no limit to the use of a dispersion aid such as a surfactant or a polymer dispersant at the time of sol formation.
【００１２】本発明において用いられる皮膜形成性を有
する樹脂（Ａ）は数１で定義されるパーマコール値〔π
，Ｍ．Ｓａｌａｍｅ；Ｆｕｔｕｒ−Ｐａｃｋ．’８５
Ｐｒｏｃｅｅｄｉｎｇｓ Ｐ１１９（’８５）参照
〕が７５Ｃａｌ／ｃ・ｃ以上である必要がある。好まし
くは、８０Ｃａｌ／ｃ・ｃ以上である。７５Ｃａｌ／ｃ
・ｃ未満では気体遮断性の付与効果が低下するので好ま
しくない。該特性を満足する樹脂としては、ポリ塩化ビ
ニリデン系樹脂、ポリアクリロニトリル系樹脂およびポ
リビニルアルコール系樹脂等が挙られる。これらの樹脂
は単独で用いても２種以上を配合して用いてもかまわな
い。The film-forming resin (A) used in the present invention has a permacol value [π
,M. Salame; Futur-Pack. '85
Refer to Proceedings P119 ('85)] must be 75 Cal/c.c or more. Preferably, it is 80 Cal/cc or more. 75Cal/c
- If it is less than c, the effect of imparting gas barrier properties will be reduced, which is not preferable. Examples of resins that satisfy these characteristics include polyvinylidene chloride resins, polyacrylonitrile resins, and polyvinyl alcohol resins. These resins may be used alone or in combination of two or more.
【００１３】本発明においては、皮膜形成性を有する樹
脂（Ａ）とカオリナイト（Ｂ）の配合組成物において、
その配合比は（Ｂ）／（Ａ）の重量比で１／９９〜９０
／１０であることが必要であり５／９５〜８０／２０で
あることが好ましい。１／９９よりその比が小さい場合
には、気体遮断性向上効果が充分でなくなるので好まし
くない。逆に、９０／１０を越えた場合は、気体遮断性
向上効果が飽和するうえに、皮膜の強度や柔軟性が低下
するので好ましくない。（Ａ）及び（Ｂ）よりなる組成
物を得るための配合方法は、公知の任意の混合方法をと
ることが可能であるが、（Ａ）及び（Ｂ）の配合効果を
最も効果的に得るためには、（Ａ）の溶液あるいは溶媒
への分散体と（Ｂ）の溶媒への分散体であるゾルとを混
合するのが好ましい態様である。溶媒としては、特に限
定はないが安全面より水系が好適である。また、（Ａ）
の溶液あるいは分散液の中で（Ｂ）を合成したり、逆に
（Ｂ）のゾルの中で（Ａ）の重合を行なうという方法も
両者の配合効果を高める方法として推奨される。混合の
ための手段も制限はなく、高速攪拌法、高圧分散法、超
音波分散法等公知の方法が任意に使用できる。これらの
方法を組合せた方法も好適である。該配合組成物には、
さらに必要に応じて他の金属酸化物系微粒子、着色剤、
静電防止剤、耐ブロッキング剤、無機または有機微粒子
よりなる滑剤、酸化防止剤等の添加剤を含有させてもか
まわない。[0013] In the present invention, in the blended composition of the film-forming resin (A) and kaolinite (B),
The blending ratio is 1/99 to 90 (B)/(A) weight ratio
/10, and preferably 5/95 to 80/20. If the ratio is smaller than 1/99, the effect of improving gas barrier properties will not be sufficient, which is not preferable. On the other hand, if it exceeds 90/10, the effect of improving gas barrier properties will be saturated and the strength and flexibility of the film will decrease, which is not preferable. Although any known mixing method can be used to obtain the composition consisting of (A) and (B), it is possible to obtain the mixing effect of (A) and (B) most effectively. In order to achieve this, it is a preferred embodiment to mix a solution or a dispersion of (A) in a solvent and a sol, which is a dispersion of (B) in a solvent. The solvent is not particularly limited, but from the viewpoint of safety, an aqueous solvent is preferred. Also, (A)
A method of synthesizing (B) in a solution or dispersion of (B) or, conversely, polymerizing (A) in a sol of (B) is also recommended as a method of enhancing the effect of blending the two. The means for mixing is also not limited, and any known methods such as high-speed stirring, high-pressure dispersion, and ultrasonic dispersion can be used. A combination of these methods is also suitable. The blended composition includes:
In addition, other metal oxide particles, colorants,
Additives such as antistatic agents, antiblocking agents, lubricants made of inorganic or organic fine particles, and antioxidants may be included.
【００１４】該配合組成物層を、基体フイルム表面に積
層する方法としては、組成物を予めフイルム状となし基
体フイルムに貼合せる方法、すなわち、ラミネート法や
、基体フイルム上に溶融押出しする押出しコーティング
法、あるいは、組成物の溶液或いは、分散液を基体フイ
ルム表面に塗布するコーティング法など公知の方法が用
いられる。コーティング法によって、基体フイルム表面
に塗布した後、乾燥、熱処理をする方法が最も好ましい
。コーティング方法としては、グラビアやリバースなど
のロールコーティング法、ドクターナイフ法やエアーナ
イフ、ノズルコーティング法など通常の方法が用い得る
。このような方法によって積層されるべき、配合組成物
層の厚みは、基体フイルム、目的とするレベル等によっ
て異なるが、通常は乾燥厚みで１０μ以下、好ましくは
５μ以下、最も好ましくは、３μ以下であることが望ま
しい。下限は特にないが、０．１μ以下である場合には
、実質的に充分な効果が得られ難い。なお、本積層を行
なう前に基体フイルムにコロナ処理その他の表面活性化
処理や、ウレタン樹脂など公知のアンカー処理剤を用い
てアンカー処理を施しても良い。[0014] Methods for laminating the blended composition layer on the surface of the base film include a method in which the composition is made into a film in advance and laminated onto the base film, that is, a lamination method, and an extrusion coating method in which the composition is melt-extruded onto the base film. A known method may be used, such as a method or a coating method in which a solution or dispersion of the composition is applied to the surface of the base film. The most preferred method is to apply the coating onto the surface of the base film, followed by drying and heat treatment. As a coating method, a conventional method such as a roll coating method such as gravure or reverse, a doctor knife method, an air knife method, or a nozzle coating method can be used. The thickness of the blended composition layer to be laminated by such a method varies depending on the base film, the desired level, etc., but is usually 10μ or less, preferably 5μ or less, and most preferably 3μ or less in dry thickness. It is desirable that there be. Although there is no particular lower limit, if it is 0.1 μ or less, it is difficult to obtain substantially sufficient effects. Note that, before performing the main lamination, the base film may be subjected to corona treatment or other surface activation treatment, or anchor treatment using a known anchor treatment agent such as urethane resin.
【００１５】[0015]
【実施例】以下、実施例により、本発明を述べる。なお
、例中の濃度表示は、特にことわらない限り、重量基準
であり、評価は以下の方法によった。
（酸素透過性）ＡＳＴＭ−Ｄ−１００３−６１に準拠し
、２５℃ドライおよび２５℃、８０％ＲＨにおいて測定
した。
（ヘイズ）ＡＳＴＭ−Ｄ−１００３−６１に準拠した。[Examples] The present invention will be described below with reference to Examples. In addition, unless otherwise specified, the concentration in the examples is based on weight, and the evaluation was performed according to the following method. (Oxygen permeability) Measured in accordance with ASTM-D-1003-61 at 25° C. dry and at 25° C. and 80% RH. (Haze) Based on ASTM-D-1003-61.
【００１６】実施例１
コロナ放電処理された厚さ２５μｍの二軸延伸ポリプロ
ピレンフイルムのコロナ処理面側にロールコーティング
方式により、共重合ポリエステルと３官能性イソシアネ
ートを４：１の割合でメチルエチルケトン／トルエンの
等量混合溶媒に溶解した溶液を乾燥後の塗布量として０
．２ｇ／ｍ２ となるように塗布、乾燥した。該処理フ
イルムの塗布面に、重合度が３００、けん化度９８．５
％のポリビニルアルコールの水溶液と、脱イオン法で精
製した平均粒径が１．０μｍである六角板状の天然のカ
オリナイトの水ゾルとをカオリナイト／ポリビニルアル
コールの重量比で０．１／０．９になるように混ぜ、高
圧均質式の分散機を用い均一分散した塗工液をロールコ
ーティング方式により乾燥後の塗布量として２．５μｍ
となるように塗布、乾燥の後１３０℃で２分間の熱処理
を行ない積層フイルムを得た。得られた積層フイルムの
特性を表１に示す。本実施例で得られた積層フイルムは
透明性に優れ、かつ、酸素ガスの遮断性が優れている。Example 1 A copolymerized polyester and a trifunctional isocyanate were coated with methyl ethyl ketone/toluene in a ratio of 4:1 on the corona-treated side of a biaxially stretched polypropylene film having a thickness of 25 μm that had been subjected to a corona discharge treatment. The coating amount after drying of the solution dissolved in an equal amount of mixed solvent is 0.
．． It was coated at a weight of 2 g/m2 and dried. The coated surface of the treated film has a polymerization degree of 300 and a saponification degree of 98.5.
% aqueous solution of polyvinyl alcohol and an aqueous sol of hexagonal plate-shaped natural kaolinite with an average particle size of 1.0 μm purified by deionization method at a weight ratio of kaolinite/polyvinyl alcohol of 0.1/0. The coating solution was mixed so as to have a coating weight of 2.5 μm after drying, and the coating solution was uniformly dispersed using a high-pressure homogenizing type dispersing machine using a roll coating method.
After coating and drying, heat treatment was performed at 130° C. for 2 minutes to obtain a laminated film. Table 1 shows the properties of the obtained laminated film. The laminated film obtained in this example has excellent transparency and oxygen gas barrier properties.
【００１７】比較例１
実施例１の方法において、カオリナイトの配合を止め、
ポリビニルアルコール水溶液のみを塗工液とする以外、
実施例１と同じ方法で得た積層フイルムの特性を表１に
示す。本比較例で得られた積層フイルムは透明性は良好
であるが、高湿度下での酸素ガス遮断性が劣る。
比較例２
実施例１の方法において、ポリビニルアルコールの配合
を止め、カオリナイトの水ゾルのみを塗工液とする以外
、実施例１と同じ方法で得た積層フイルムの特性を表１
に示す。本比較例で得られた積層フイルムは、酸素ガス
遮断性が劣る。
比較例３
実施例１の方法において用いた積層前の二軸延伸ポリプ
ロピレンフイルムの特性を表１に示す。本比較例のフイ
ルムは透明性は良好であるが、酸素ガス遮断性が著るし
く劣る。Comparative Example 1 In the method of Example 1, the addition of kaolinite was stopped,
In addition to using only polyvinyl alcohol aqueous solution as the coating liquid,
Table 1 shows the properties of the laminated film obtained by the same method as in Example 1. Although the laminated film obtained in this comparative example has good transparency, it has poor oxygen gas barrier properties under high humidity. Comparative Example 2 Table 1 shows the properties of a laminated film obtained in the same manner as in Example 1, except that the blending of polyvinyl alcohol was stopped and only the kaolinite aqueous sol was used as the coating liquid.
Shown below. The laminated film obtained in this comparative example has poor oxygen gas barrier properties. Comparative Example 3 Table 1 shows the properties of the biaxially stretched polypropylene film used in the method of Example 1 before lamination. Although the film of this comparative example has good transparency, its oxygen gas barrier properties are significantly inferior.
【００１８】実施例２
実施例１の方法において、脱イオン精製したカオリナイ
トの平均粒径およびカオリナイトとポリビニルアルコー
ルとの配合比を表１に示すごとく変更する以外、実施例
１と同じ方法で得た積層フイルムの特性を表１に示す。
本実施例で得られた積層フイルムも透明性に優れ、かつ
、酸素ガスの遮断性が優れている。
実施例３
実施例１の方法において基体フイルムを１２μｍの二軸
延伸ポリエステルフイルムとし、皮膜形成樹脂としてポ
リ塩化ビニリデン系共重合樹脂を用い、表１に示した配
合組成物比で、かつ、配合組成物の塗布量を乾燥後で３
．５μｍの厚みになるように変更する以外、実施例１と
同じ方法で得た積層フイルムの特性を表１に示す。本実
施例で得られた積層フイルムも透明性に優れ、かつ、酸
素ガスの遮断性が優れている。Example 2 The same method as in Example 1 was used except that the average particle size of deionized and purified kaolinite and the blending ratio of kaolinite and polyvinyl alcohol were changed as shown in Table 1. Table 1 shows the properties of the obtained laminated film. The laminated film obtained in this example also has excellent transparency and oxygen gas barrier properties. Example 3 In the method of Example 1, a 12 μm biaxially stretched polyester film was used as the base film, a polyvinylidene chloride copolymer resin was used as the film-forming resin, and the composition ratio was as shown in Table 1. After drying, reduce the amount of application to 3.
．． Table 1 shows the properties of the laminated film obtained in the same manner as in Example 1 except that the thickness was changed to 5 μm. The laminated film obtained in this example also has excellent transparency and oxygen gas barrier properties.
【００１９】比較例４
実施例３の方法でカオリナイトの水ゾルの配合を止め、
ポリ塩化ビニリデン系共重合樹脂の水分散液のみを塗工
液とする以外、実施例３と同じ方法で得た積層フイルム
の特性を表１に示す。本比較例で得られた積層フイルム
は、高湿度下での酸素ガス遮断性が実施例３の積層フイ
ルムに比で劣っており、カオリナイトの配合効果が顕著
であることがわかる。Comparative Example 4 By the method of Example 3, the addition of kaolinite aqueous sol was stopped,
Table 1 shows the properties of a laminated film obtained in the same manner as in Example 3, except that only the aqueous dispersion of polyvinylidene chloride copolymer resin was used as the coating liquid. It can be seen that the laminated film obtained in this comparative example had inferior oxygen gas barrier properties under high humidity compared to the laminated film of Example 3, and that the effect of blending kaolinite was remarkable.
【００２０】実施例４
実施例１の方法において、皮膜形成樹脂としてポリビニ
ルアルコールとポリ塩化ビニリデンとの共重合体樹脂（
ポリビニルアルコール単位／ポリ塩化ビニリデン単位の
比は重量比で９／１）を用いる以外、実施例１と同じ方
法で得た積層フイルムの特性を表１に示す。本実施例で
得られた積層フイルムも透明性に優れ、かつ、酸素ガス
の遮断性に優れている。Example 4 In the method of Example 1, a copolymer resin of polyvinyl alcohol and polyvinylidene chloride (
Table 1 shows the properties of a laminated film obtained in the same manner as in Example 1, except that the ratio of polyvinyl alcohol units to polyvinylidene chloride units was 9/1 by weight. The laminated film obtained in this example also has excellent transparency and oxygen gas barrier properties.
【００２１】比較例５
実施例４の方法において、カオリナイトの水ゾルの配合
を止める以外、実施例３と同じ方法で得た積層フイルム
の特性を表１に示す。本比較例で得られた積層フイルム
は、高湿度下での酸素ガス遮断性が実施例４の積層フイ
ルムに比べ劣っており、カオリナイトの配合効果が顕著
であることがわかる。Comparative Example 5 Table 1 shows the properties of a laminated film obtained in the same manner as in Example 3, except that the addition of the kaolinite aqueous sol was stopped. It can be seen that the laminated film obtained in this comparative example has inferior oxygen gas barrier properties under high humidity compared to the laminated film of Example 4, and that the effect of incorporating kaolinite is significant.
【００２２】実施例５
実施例２の方法において、皮膜形成樹脂としてポリビニ
ルアルコールに替え、ポリ（エチレンビニルアルコール
）共重合体として、かつ、配合組成物の塗布量を乾燥後
で３．５μｍの厚みになるように変更する以外、実施例
２と同じ方法で得た積層フイルムの特性を表１に示す。
本実施例で得られた積層フイルムも透明性に優れ、かつ
、酸素ガスの遮断性に優れている。
比較例６
実施例５の方法において、カオリナイトの水ゾルの配合
を止める以外、実施例５と同じ方法で得た積層フイルム
の特性を表１に示す。本比較例で得られた積層フイルム
は、高湿度下での酸素ガス遮断性が実施例５の積層フイ
ルムに比べ劣っており、カオリナイトの配合効果が顕著
であることがわかる。Example 5 In the method of Example 2, poly(ethylene vinyl alcohol) copolymer was used instead of polyvinyl alcohol as the film-forming resin, and the coating amount of the blended composition was changed to a thickness of 3.5 μm after drying. Table 1 shows the properties of the laminated film obtained in the same manner as in Example 2 except for the following changes. The laminated film obtained in this example also has excellent transparency and oxygen gas barrier properties. Comparative Example 6 Table 1 shows the properties of a laminated film obtained in the same manner as in Example 5 except that the addition of the kaolinite aqueous sol was stopped. It can be seen that the laminated film obtained in this comparative example has inferior oxygen gas barrier properties under high humidity compared to the laminated film of Example 5, and that the effect of incorporating kaolinite is significant.
【００２３】実施例６
基体フイルムとして１５μｍの二軸延伸ナイロンフイル
ムを、皮膜形成樹脂としてポリビニルアルコールとポリ
塩化ビニリデン共重合体との１：１の混合物（重量比）
を用いる以外、実施例３と同じ方法で得た積層フイルム
の特性を表１に示す。本実施例で得られた積層フイルム
も、透明性に優れ、かつ、酸素ガス遮断性に優れている
。Example 6 A 15 μm biaxially stretched nylon film was used as the base film, and a 1:1 mixture (weight ratio) of polyvinyl alcohol and polyvinylidene chloride copolymer was used as the film-forming resin.
Table 1 shows the properties of a laminated film obtained in the same manner as in Example 3, except that . The laminated film obtained in this example also has excellent transparency and oxygen gas barrier properties.
【００２４】比較例７
実施例６の方法において、カオリナイトの配合を止める
以外、実施例６と同じ方法で得た積層フイルムの特性を
表１に示す。本比較例で得られた積層フイルムは、高湿
度下での酸素ガスの遮断性が実施例６の積層フイルムに
比べ劣っており、カオリナイトの配合効果が顕著である
ことがわかる。Comparative Example 7 Table 1 shows the properties of a laminated film obtained in the same manner as in Example 6, except that the addition of kaolinite was omitted. It can be seen that the laminated film obtained in this comparative example has inferior oxygen gas barrier properties under high humidity compared to the laminated film of Example 6, and that the effect of incorporating kaolinite is remarkable.
【００２５】[0025]
【表１】[Table 1]
【００２６】[0026]
【表２】[Table 2]
【００２７】[0027]
【発明の効果】以上実施例で示した通り本発明法は、透
明で、かつ高度の気体の遮断性を有するフイルムを提供
するものであり、食品包装、薬品や医療器具などの無菌
包装、電気、機械部品等の包装に広く活用できる。Effects of the Invention As shown in the examples above, the method of the present invention provides a film that is transparent and has a high degree of gas barrier property, and can be used for food packaging, aseptic packaging for drugs and medical instruments, and for electrical appliances. It can be widely used for packaging machine parts, etc.
Claims (1)
少くとも片面に、下記一般式で定義されるパーマコール
値（π）が７５ｃａｌ／ｃｃ以上である皮膜形成性を有
する樹脂（Ａ）とカオリナイト（Ｂ）とよりなる組成物
とからなり、（Ｂ）／（Ａ）の重量比が１／９９〜９０
／１０であるごとく配合された組成物よりなる層が形成
されてなるガスバリアー性フイルム。 【数１】 （ここで、δはポリマー鎖の凝集力、ｆｖはフリーボリ
ウム）[Claim 1] A resin (A) having film-forming properties having a permacol value (π) defined by the following general formula of 75 cal/cc or more and kaolinite on at least one side of a base film made of a thermoplastic resin. (B) and a composition consisting of (B) and a composition consisting of (B)/(A) in a weight ratio of 1/99 to 90.
A gas barrier film formed with a layer made of a composition blended so as to have a ratio of 10 to 10. [Equation 1] (Here, δ is the cohesive force of the polymer chain, fv is the free volume)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5608591A JPH04270650A (en) | 1991-02-26 | 1991-02-26 | Gas barrier-type film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5608591A JPH04270650A (en) | 1991-02-26 | 1991-02-26 | Gas barrier-type film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04270650A true JPH04270650A (en) | 1992-09-28 |
Family
ID=13017252
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5608591A Pending JPH04270650A (en) | 1991-02-26 | 1991-02-26 | Gas barrier-type film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04270650A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7404999B2 (en) | 2004-09-30 | 2008-07-29 | Graphic Packaging International, Inc. | Anti-blocking barrier composite |
| US7416767B2 (en) * | 2004-09-30 | 2008-08-26 | Graphic Packaging International, Inc. | Anti-blocking coatings for PVdc-coated substrates |
-
1991
- 1991-02-26 JP JP5608591A patent/JPH04270650A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7404999B2 (en) | 2004-09-30 | 2008-07-29 | Graphic Packaging International, Inc. | Anti-blocking barrier composite |
| US7416767B2 (en) * | 2004-09-30 | 2008-08-26 | Graphic Packaging International, Inc. | Anti-blocking coatings for PVdc-coated substrates |
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