JP3168201B2 - Heat shrinkable packaging film - Google Patents
Heat shrinkable packaging filmInfo
- Publication number
- JP3168201B2 JP3168201B2 JP30742499A JP30742499A JP3168201B2 JP 3168201 B2 JP3168201 B2 JP 3168201B2 JP 30742499 A JP30742499 A JP 30742499A JP 30742499 A JP30742499 A JP 30742499A JP 3168201 B2 JP3168201 B2 JP 3168201B2
- Authority
- JP
- Japan
- Prior art keywords
- heat
- film
- shrinkable
- layer
- wrinkles
- 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.)
- Expired - Lifetime
Links
- 239000012785 packaging film Substances 0.000 title claims description 66
- 229920006280 packaging film Polymers 0.000 title claims description 66
- 229920006257 Heat-shrinkable film Polymers 0.000 claims description 121
- 239000010410 layer Substances 0.000 claims description 74
- 229910052751 metal Inorganic materials 0.000 claims description 52
- 239000002184 metal Substances 0.000 claims description 52
- 239000010409 thin film Substances 0.000 claims description 51
- 239000012790 adhesive layer Substances 0.000 claims description 36
- 239000011347 resin Substances 0.000 claims description 20
- 229920005989 resin Polymers 0.000 claims description 20
- 230000037303 wrinkles Effects 0.000 description 60
- 239000010408 film Substances 0.000 description 43
- 239000000853 adhesive Substances 0.000 description 39
- 230000001070 adhesive effect Effects 0.000 description 39
- 239000002932 luster Substances 0.000 description 18
- 230000000903 blocking effect Effects 0.000 description 15
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 12
- 238000006073 displacement reaction Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- -1 polyethylene Polymers 0.000 description 8
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- 229920006300 shrink film Polymers 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 238000007756 gravure coating Methods 0.000 description 5
- 238000000576 coating method Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 235000021443 coca cola Nutrition 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
Landscapes
- Packages (AREA)
- Closures For Containers (AREA)
- Wrappers (AREA)
- Laminated Bodies (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、金属光沢に優れた
熱収縮性包装用フイルム、特に瓶のキャップシールや胴
ラベルに使用する熱収縮性包装用フイルムに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-shrinkable packaging film excellent in metallic luster, and more particularly to a heat-shrinkable packaging film used for cap seals and body labels on bottles.
【０００２】[0002]
【従来の技術】熱収縮させるとランダムな形状のしわを
現出させ、瓶のキャップシールや胴ラベルに使用可能な
金属光沢を有する熱収縮性包装用フイルムが知られてい
る。例えば、特公平７−４１７００号公報には、熱収縮
性フイルム、接着剤層、金属薄膜、低伸度樹脂層、高伸
度樹脂層が順次積層されたシュリンクフイルムが記載さ
れている。このシュリンクフイルムを熱収縮すると、金
属薄膜の存在により金属光沢を有した石垣状の収縮外観
を呈する。また、熱収縮させるとランダムな形状のしわ
を現出させ、瓶のキャップシールや胴ラベルに使用可能
な金属光沢を有する熱収縮性包装用フイルムであって、
熱収縮性フイルムと金属光沢を有する非熱収縮性フイル
ムとを接着剤で全面に貼り合わせた構成のものが知られ
ている。例えば、特開昭５３−１１３８７４号公報に
は、熱収縮性フイルムと、熱収縮性フイルムより熱収縮
性の少ない低収縮性フイルムに金属蒸着を施してその非
蒸着面とを接着剤で全面に貼り合わせた熱収縮性積層フ
イルムが記載されていて、その特許請求の範囲の欄に
は、６０℃における接着剤の剪断接着強さが３．５Ｋｇ
／１５ｍｍ巾以下である記載がある。そして、特開昭５
３−１１３８７４号公報に記載の技術における接着剤の
剪断接着強さは、具体的には、その実施例１〜９の記載
から明らかなように、３．１〜０．６Ｋｇ／１５ｍｍ巾
であって、非常に強いものである。この熱収縮性積層フ
イルムを熱収縮させると、金属薄膜の存在により金属光
沢を有するしわを形成する。2. Description of the Related Art A heat-shrinkable packaging film having a metallic luster that can be used for a cap seal or a body label of a bottle, which causes random wrinkles to appear upon heat shrinkage is known. For example, Japanese Patent Publication No. 7-41700 describes a shrink film in which a heat-shrinkable film, an adhesive layer, a metal thin film, a low elongation resin layer, and a high elongation resin layer are sequentially laminated. When this shrink film is thermally shrunk, it exhibits a stone wall-like shrink appearance having a metallic luster due to the presence of the metal thin film. In addition, a heat-shrinkable packaging film having a metallic luster that can be used for a cap seal or a body label of a bottle to appear wrinkles of a random shape when heat shrunk,
There is known a configuration in which a heat-shrinkable film and a non-heat-shrinkable film having a metallic luster are bonded to each other with an adhesive. For example, JP-A-53-113874 discloses that a metal film is deposited on a heat-shrinkable film and a low-shrinkage film having less heat shrinkage than the heat-shrinkable film, and the non-evaporated surface is entirely coated with an adhesive. The laminated heat-shrinkable laminated film is described, and in the claims section, the shear adhesive strength of the adhesive at 60 ° C. is 3.5 kg.
/ 15 mm width or less. And, JP
Specifically, the shear adhesive strength of the adhesive in the technique described in JP-A-3-113874 is 3.1 to 0.6 kg / 15 mm width, as is apparent from the description of Examples 1 to 9. And very strong. When the heat-shrinkable laminated film is heat-shrinked, wrinkles having metallic luster are formed due to the presence of the metal thin film.
【０００３】[0003]
【発明が解決しようとする課題】しかし、特公平７−４
１７００号公報に記載のシュリンクフイルムには、以下
に示す欠点があった。 （１）シュリンクフイルムを熱収縮すると金属光沢を有
した石垣状の収縮外観を呈するが、石垣状を形どる大き
いしわの間に無数の小さいクラックが存在するため、全
体としてやや金属光沢に欠けるものであった。 （２）シュリンクフイルムは、基材となるフイルムは熱
収縮性フイルムだけであり、非熱収縮性フイルムが存在
せず、熱収縮性フイルムを表層にして使用しなければな
らず、収縮により現出するしわは熱収縮性フイルムの内
側に存在しているので、立体的でなかった。However, Japanese Patent Publication No. Hei 7-4
The shrink film described in Japanese Patent No. 1700 has the following disadvantages. (1) When shrink film is thermally shrunk, it exhibits a stone wall-like shrink appearance with a metallic luster, but there are innumerable small cracks between large wrinkles forming the stone wall, so that the whole lacks a little metallic luster. Met. (2) The shrink film is a heat-shrinkable film only as a base material, no non-heat-shrinkable film exists, and the heat-shrinkable film must be used as a surface layer, and appears due to shrinkage. The wrinkles were not three-dimensional because they existed inside the heat-shrinkable film.
【０００４】また、特開昭５３−１１３８７４号公報に
記載の熱収縮性積層フイルムには、以下に示す欠点があ
った。 （３）６０℃における接着剤の剪断接着強さが３．１〜
０．６Ｋｇ／１５ｍｍ巾のように強いと、熱収縮時に接
着剤と熱収縮性フイルム、及び低収縮性フイルムとの貼
り合わせ面のずれが小さくなるので、熱収縮性積層フイ
ルムの収縮を阻害してしまい、収縮が不十分になった
り、収縮に要する時間が長くなったりした。また、収縮
により現出するしわも、立体的ではあるが剪断接着強さ
が強いために、全体に満遍なくしわが現出せずに、局部
的に大きなしわや低収縮性フイルムの剥離によるうきが
発生したり、場合によっては低収縮性フイルムが破れた
りする問題があり、意匠性にも欠けていた。上記の欠点
は、収縮率が大きくなる程さらに顕著であり、例えば熱
収縮性積層フイルムを一升瓶のキャップシールとして使
用した場合には、一升瓶の口部と胴部とで円周が異なる
ので、当然熱収縮した時には口部と胴部とで収縮率が異
なり、そのために、低収縮の胴部では、比較的満遍なく
しわが現出するが、高収縮の口部では、局部的に大きな
しわや低収縮性フイルムの剥離によるうきが発生した
り、場合によっては低収縮性フイルムが破れたりする問
題があり、意匠性にも欠けていた。 （４）６０℃における接着剤の剪断接着強さを３．１〜
０．６Ｋｇ／１５ｍｍ巾に設定するには、接着剤の厚さ
を１５〜２０μｍ程度にする必要があり、かなり厚かっ
た。このように接着剤の厚さを厚くすると、接着剤が経
時で熱収縮性積層フイルムの断面からはみ出して、所謂
ブロッキングが発生した。従って、熱収縮性積層フイル
ムをセンターシールによりチューブ状にした後、裁断し
たものを重ねたり、裁断後予備成形したものを重ねたり
するとブロッキングにより離れなくなる問題があった。
特に、熱収縮性積層フイルムをスリット工程後やセンタ
ーシール工程後にチューブ状のものをロール状態で保管
しておくと、次工程で熱収縮性積層フイルムを巻き出す
時に、ブロッキングの発生により熱収縮性積層フイルム
が破れたり、切れたりする問題があった。従って、予備
成形用のキャップシールはもちろん、ロール状態での保
管が必要な自動機装填用のキャップシール等には、全く
使用できなかった。 （５）実施例２〜９の記載からから明らかなように、金
属蒸着を施した低収縮性フイルムは、非蒸着面が熱収縮
性フイルムと貼り合わされており、金属蒸着層は実際に
は表層に形成されている。従って、金属蒸着層に容易に
傷がついたり、経時で金属蒸着層が容易に腐食したりす
る問題があった。上記の問題を解決するために蒸着面と
貼り合わすと、接着剤の剪断強さが３．１〜０．６Ｋｇ
／１５ｍｍ巾であり、非常に強いことから、金属蒸着層
にストレスがかかり、熱収縮性積層フイルムの加工時や
熱収縮時に金属蒸着層と低収縮性フイルムの間で容易に
剥離が生じるという問題もあった。The heat-shrinkable laminated film described in JP-A-53-113874 has the following disadvantages. (3) The shear adhesive strength of the adhesive at 60 ° C. is 3.1 to 3.1.
If the strength is as strong as 0.6 kg / 15 mm width, the displacement of the bonding surface between the adhesive and the heat-shrinkable film or the low-shrinkage film during the heat shrinkage becomes small, so that the shrinkage of the heat-shrinkable laminated film is hindered. As a result, the shrinkage became insufficient or the time required for the shrinkage increased. Also, wrinkles that appear due to shrinkage are three-dimensional but have strong shear adhesive strength, so that wrinkles do not appear evenly throughout the whole, but large wrinkles locally and wrinkles due to peeling of low shrinkage film occur In some cases, the low shrinkage film is broken, and the design is lacking. The above-mentioned disadvantages are more remarkable as the shrinkage ratio increases.For example, when a heat-shrinkable laminated film is used as a cap seal for a single-shoulder bottle, the circumference differs between the mouth and the body of the single-shoulder bottle. When heat shrinks, the shrinkage rate differs between the mouth and the torso. For this reason, wrinkles appear relatively evenly in the low shrinkage of the torso, but locally large wrinkles and low wrinkles appear in the high shrinkage of the mouth. There was a problem that peeling of the shrinkable film caused the peeling, and in some cases, the low shrinkable film was broken, and the design was lacking. (4) The shear adhesive strength at 60 ° C. of 3.1 to
In order to set the width to 0.6 kg / 15 mm width, the thickness of the adhesive had to be about 15 to 20 μm, which was quite thick. When the thickness of the adhesive was increased, the adhesive protruded from the cross section of the heat-shrinkable laminated film with the passage of time, so-called blocking occurred. Therefore, when the heat-shrinkable laminated film is formed into a tube shape by a center seal and then cut and stacked, or preformed after being cut and stacked, there is a problem that the heat-shrinkable laminated film cannot be separated due to blocking.
In particular, if the heat-shrinkable laminated film is stored in a roll state after the slitting process or the center sealing process, when the heat-shrinkable laminated film is unwound in the next process, heat shrinkage due to blocking occurs. There was a problem that the laminated film was torn or cut. Therefore, it could not be used as a cap seal for pre-molding or a cap seal for automatic machine loading which needs to be stored in a roll state. (5) As is clear from the description of Examples 2 to 9, the low-shrinkable film on which metal has been deposited has a non-deposited surface bonded to a heat-shrinkable film, and the metal-deposited layer is actually a surface layer. Is formed. Therefore, there has been a problem that the metal deposition layer is easily damaged or the metal deposition layer is easily corroded with time. When bonded to a vapor deposition surface to solve the above problem, the shear strength of the adhesive is 3.1 to 0.6 kg.
/ 15 mm width, which is very strong, so that stress is applied to the metal vapor deposited layer, and the peeling easily occurs between the metal vapor deposited layer and the low shrink film during processing of the heat shrinkable laminated film or heat shrinkage. There was also.
【０００５】以上（１）〜（５）の欠点から明らかなよ
うに、従来のシュリンクフイルムや熱収縮性積層フイル
ムは、特に瓶のキャップシールや胴ラベルに使用した場
合、全く実用に耐えるものではなかった。本発明は、上
記（１）〜（５）に示した全ての欠点を解決したもので
ある。As is apparent from the above-mentioned drawbacks (1) to (5), conventional shrink films and heat-shrinkable laminated films are not practically usable especially when used for cap seals or body labels. Did not. The present invention has solved all the disadvantages shown in the above (1) to (5).
【０００６】[0006]
【課題を解決するための手段】本発明は、熱収縮性フイ
ルム、粘着層、金属薄膜層、非熱収縮性フイルムを順次
積層してなるものであって、熱収縮性フイルムと金属薄
膜層を設けた非熱収縮性フイルムとを金属薄膜層を内側
にして厚さ０．５〜５μｍの粘着層で貼り合わせたこ
と、及び熱収縮性フイルムと非熱収縮性フイルムとの密
着強度が１０〜５００ｇ／１５ｍｍであることを特徴と
する熱収縮性包装用フイルムである。本発明は、金属薄
膜層と非熱収縮性フイルムとの間に樹脂層を形成してな
る上記の熱収縮性包装用フイルムである。また、本発明
は、熱収縮性フイルムの厚さが３０〜７０μｍであり、
かつ非熱収縮性フイルムの厚さが３〜１２μｍであるこ
れらの熱収縮性包装用フイルムである。According to the present invention, a heat-shrinkable film, an adhesive layer, a metal thin film layer, and a non-heat-shrinkable film are sequentially laminated, wherein the heat-shrinkable film and the metal thin film layer are laminated. The provided non-heat-shrinkable film was bonded to the non-heat-shrinkable film with the adhesive layer having a thickness of 0.5 to 5 μm with the metal thin film layer inside, and the adhesion strength between the heat-shrinkable film and the non-heat-shrinkable film was 10 to 10. A heat shrinkable packaging film characterized by a weight of 500 g / 15 mm. The present invention is the above heat-shrinkable packaging film comprising a resin layer formed between a metal thin film layer and a non-heat-shrinkable film. In the present invention, the thickness of the heat-shrinkable film is 30 to 70 μm,
These heat-shrinkable packaging films have a non-heat-shrinkable film thickness of 3 to 12 μm.
【０００７】本発明の熱収縮性包装用フイルムは、熱収
縮すると全体に満遍なくしわが現出するが、しわとしわ
の間にクラックが発生しないので優れた金属光沢を有す
る。The heat-shrinkable packaging film of the present invention shows wrinkles evenly when heat-shrinked, but has excellent metallic luster because cracks do not occur between wrinkles.
【０００８】また、本発明の熱収縮性包装用フイルム
は、非熱収縮性フイルムが外側に存在するので、熱収縮
により現出するしわが非常に立体的である。In the heat-shrinkable packaging film of the present invention, since the non-heat-shrinkable film is present on the outside, wrinkles appearing due to heat shrinkage are very three-dimensional.
【０００９】本発明の熱収縮性包装用フイルムは、熱収
縮性フイルムと、金属薄膜層を形成した非熱収縮性フイ
ルムとを金属薄膜層を内側にして、厚さ０．５〜５μｍ
の粘着層で全面に貼り合わせてあり、熱収縮性フイルム
と非熱収縮性フイルムの密着強度が１０〜５００ｇ／１
５ｍｍとなるように、粘着層を調整した。熱収縮性フイ
ルムと非熱収縮性フイルムの密着強度が１０〜５００ｇ
／１５ｍｍと弱いので、熱収縮時に、粘着層自身のず
れ、粘着層と熱収縮性フイルムとの貼り合わせ面のず
れ、又は粘着層と金属薄膜層との貼り合わせ面のずれが
適度に大きいので、熱収縮性包装用フイルムの収縮を阻
害せず、収縮が十分に行われ、収縮に要する時間も短く
てすむ。また、収縮により現出するしわも、密着強度が
弱いために、立体的で、かつランダムな形状で、全体に
満遍なく現出し、局部的に大きなしわや非熱収縮性フイ
ルムの剥離によるうきが発生したり、場合によっては非
熱収縮性フイルムが破れたりすることもなく、意匠性に
も富んでいる。従って、収縮率が大きくなっても現出す
るしわには特に影響がなく、例えば熱収縮性包装用フイ
ルムを一升瓶のキャップシールとして使用した場合で
も、低収縮の胴部と高収縮の口部とで現出するしわに差
異はなく、何れも立体的で、かつランダムな形状で、全
体に満遍なくしわが現出するので意匠性にも富んでい
る。また、しわとしわの間にはクラックが生じないの
で、金属光沢は収縮の後でも低下しない。The heat-shrinkable film for packaging according to the present invention comprises a heat-shrinkable film and a non-heat-shrinkable film on which a metal thin film layer is formed, with a thickness of 0.5 to 5 μm with the metal thin film layer inside.
The adhesive strength of the heat-shrinkable film and the non-heat-shrinkable film is 10 to 500 g / 1.
The pressure-sensitive adhesive layer was adjusted to be 5 mm. Adhesion strength between heat-shrinkable film and non-heat-shrinkable film is 10 to 500 g
/ 15 mm, the displacement of the adhesive layer itself, the displacement of the bonding surface between the adhesive layer and the heat-shrinkable film, or the displacement of the bonding surface between the adhesive layer and the metal thin film layer during heat shrinkage are moderately large. Further, the shrinkage of the heat shrinkable packaging film is not hindered, the shrinkage is sufficiently performed, and the time required for the shrinkage is short. In addition, wrinkles that appear due to shrinkage, due to the low adhesion strength, appear in a three-dimensional and random shape evenly throughout, causing large wrinkles locally and wrinkles due to peeling of non-heat-shrinkable film. In addition, the non-heat-shrinkable film is not broken, and the design is rich. Therefore, even if the shrinkage rate becomes large, there is no particular effect on the wrinkles that appear, and for example, even when the heat shrinkable packaging film is used as a cap seal for a single bottle, a low shrinkage trunk and a high shrinkage mouth are used. There is no difference in the appearance of wrinkles, and each of them is three-dimensional and has a random shape. Further, since no crack occurs between wrinkles, the metallic luster does not decrease even after shrinkage.
【００１０】本発明の熱収縮性包装用フイルムは、粘着
層が厚さ０．５〜５μｍと薄いので、粘着層が経時で熱
収縮性包装用フイルムの断面からはみ出して、所謂ブロ
ッキングが発生することもない。従って、熱収縮性包装
用フイルムをセンターシールによりチューブ状にした
後、裁断したものを重ねたり、裁断後予備成形したもの
を重ねてもブロッキングにより離れなくなる問題はな
い。特に、熱収縮性包装用フイルムをスリット工程後や
センターシール工程後にチューブ状のものをロール状態
で保管しておいても、次工程で熱収縮性包装用フイルム
を巻き出す時に、ブロッキングの発生により熱収縮性包
装用フイルムが破れたり、切れたりする問題もなく保存
安定性が非常に向上した。従って、予備成形用のキャッ
プシールはもちろん、ロール状態での保管が必要な自動
機装填用のキャップシール等にも、使用可能となった。In the heat-shrinkable packaging film of the present invention, since the adhesive layer is as thin as 0.5 to 5 μm, the adhesive layer protrudes from the cross-section of the heat-shrinkable packaging film with time, so-called blocking occurs. Not even. Therefore, even if the heat-shrinkable packaging film is formed into a tube shape by a center seal and then cut and stacked, or preformed after being cut and stacked, there is no problem that the heat-shrinkable packaging film is not separated due to blocking. In particular, even if the heat-shrinkable packaging film is stored in a rolled state after the slitting step or the center sealing step, when the heat-shrinkable packaging film is unwound in the next step, the film may be blocked. The storage stability was greatly improved without the problem of the heat shrinkable packaging film being broken or broken. Therefore, it can be used not only as a cap seal for preforming, but also as a cap seal for automatic machine loading which needs to be stored in a roll state.
【００１１】また、金属薄膜層を設けた非熱収縮性フイ
ルムは、金属薄膜層面が熱収縮性フイルムと貼り合わさ
れており、金属薄膜層が表層ではなく内側に存在するの
で、金属薄膜層に容易に傷がついたり、経時で金属薄膜
層が容易に腐食したりする問題がない。さらに、熱収縮
性フイルムと非熱収縮性フイルムの密着強度が１０〜５
００ｇ／１５ｍｍと弱いので、金属薄膜層面を内側にし
て貼り合わせても、金属薄膜層にストレスがかからない
ので、熱収縮性包装用フイルムの熱収縮時や製造時に金
属薄膜層と非熱収縮性フイルムの間で容易に剥離が生じ
るという問題もない。以上のように、本発明の熱収縮性
包装用フイルムは、十分に実用に耐えるものである。In the non-heat-shrinkable film provided with the metal thin film layer, the surface of the metal thin film is bonded to the heat-shrinkable film, and the metal thin film layer exists not on the surface but on the inside. There is no problem that the metal thin film layer is damaged or the metal thin film layer is easily corroded with time. Further, the adhesive strength between the heat-shrinkable film and the non-heat-shrinkable film is 10 to 5
Since the metal thin film layer is weak, ie, 00 g / 15 mm, no stress is applied to the metal thin film layer even when the films are bonded together with the metal thin film layer side facing inward. There is no problem that separation easily occurs between the two. As described above, the heat-shrinkable packaging film of the present invention sufficiently withstands practical use.
【００１２】[0012]
【発明の実施の形態】本発明に使用する熱収縮性フイル
ムは、１０％以上の熱収縮性を有するフイルムを使用す
るのが好ましく、一般に熱収縮性フイルムとして市販さ
れるフイルムが何れも適用でき、例えばポリ塩化ビニ
ル、ポリエチレン、ポリプロピレン、ポリエチレンテレ
フタレート等からなるフイルムが使用できる。熱収縮性
フイルムの厚さは、３０〜７０μｍであり、好ましくは
３０〜６０μｍ、さらに自動機装填用のキャップシール
に使用する場合には３０〜５０μｍが特に好ましい。熱
収縮性フイルムの厚さが３０μｍより薄いと、所謂こし
が弱くなり、従って熱収縮性包装用フイルムとしての機
械的強度が弱くなるので、例えば、熱収縮性包装用フイ
ルムの予備成形品を重ねると、つぶれたり、しわが生じ
たりするので好ましくない。熱収縮性フイルムの厚さが
７０μｍより厚いと、所謂こしが強くなり、熱収縮性包
装用フイルムの製造時の機械適性に欠け、作業性が悪く
なる。また、コストも高くなるので好ましくない。熱収
縮性フイルムの厚さが３０〜６０μｍであれば、機械的
強度、及び製造時の機械適性に特に優れており、３０〜
５０μｍにすると自動機装填用のキャップシール等には
最適である。DESCRIPTION OF THE PREFERRED EMBODIMENTS As the heat-shrinkable film used in the present invention, it is preferable to use a film having a heat-shrinkability of 10% or more, and any film commercially available as a heat-shrinkable film can be used. For example, a film made of polyvinyl chloride, polyethylene, polypropylene, polyethylene terephthalate, or the like can be used. The thickness of the heat-shrinkable film is 30 to 70 µm, preferably 30 to 60 µm, and particularly preferably 30 to 50 µm when used for a cap seal for automatic machine loading. When the thickness of the heat-shrinkable film is less than 30 μm, the so-called stiffness is weakened, and therefore the mechanical strength of the heat-shrinkable packaging film is weakened. This is not preferred because it causes crushing and wrinkling. If the thickness of the heat-shrinkable film is greater than 70 μm, the so-called stiffness becomes strong, and the heat-shrinkable packaging film lacks mechanical aptitude at the time of production, resulting in poor workability. Further, the cost is undesirably increased. If the thickness of the heat-shrinkable film is 30 to 60 μm, it is particularly excellent in mechanical strength and mechanical suitability during production.
When it is set to 50 μm, it is most suitable for a cap seal or the like for automatic machine loading.
【００１３】本発明に使用する非熱収縮性フイルムは、
１０％より小さい熱収縮性を有するフイルムを使用する
のが好ましく、一般に市販されるフイルムが何れも適用
でき、例えばポリエチレンテレフタレート、ポリエチレ
ンナフタレートポリエチレン、ポリプロピレン、アクリ
ル等からなるフイルムが使用できる。非熱収縮性フイル
ムの厚さは、３〜１２μｍが好ましい。本発明の熱収縮
性包装用フイルムを熱収縮した時に現出するしわは、非
熱収縮性フイルムの厚さが厚いとしわとしわの間隔が広
がり、非熱収縮性フイルムの厚さが薄いとしわししわの
間隔が狭くなって、しわの数が多くなるので、非熱収縮
性フイルムの厚さを選択することにより、適宜の収縮外
観を得ることができる。しわとしわの間隔が変化して
も、しわとしわの間にクラックが生じないので、金属光
沢は収縮の後やフイルムの厚さで低下しない。非熱収縮
性フイルムの厚さが３μｍより薄いとしわの数が多くな
りすぎて、しわとしわの間にクラックが発生し易くな
り、金属光沢が低下するので意匠性に欠け、また非熱収
縮性フイルムの金属薄膜層形成時や、樹脂層の塗工時に
しわ等が生じて作業性が悪くなるので好ましくない。非
熱収縮性フイルムの厚さが１２μｍより厚いとしわの数
が少なくなりすぎてけばけばしくなり、意匠性に欠ける
ので好ましくない。また、例えばキャップシールに使用
した場合には、天部分で熱収縮性フイルムと非熱収縮性
フイルムが剥離する、所謂天立ちが発生するので好まし
くない。天立ち防止の観点から、非熱収縮性フイルムの
厚さは３〜９μｍがより好ましく、特に３〜６μｍが最
も好ましい。The non-heat-shrinkable film used in the present invention comprises:
It is preferable to use a film having a heat shrinkability of less than 10%, and any commercially available film can be used, and for example, a film made of polyethylene terephthalate, polyethylene naphthalate polyethylene, polypropylene, acrylic, or the like can be used. The thickness of the non-heat-shrinkable film is preferably 3 to 12 μm. The wrinkles that appear when the heat-shrinkable packaging film of the present invention is heat-shrinked are as follows: when the thickness of the non-heat-shrinkable film is large, the interval between the wrinkles is widened, and when the thickness of the non-heat-shrinkable film is small. Since the interval between wrinkles becomes narrow and the number of wrinkles increases, an appropriate shrink appearance can be obtained by selecting the thickness of the non-heat-shrinkable film. Even if the distance between the wrinkles and the wrinkles changes, no crack occurs between the wrinkles and the wrinkles, so that the metallic luster does not decrease after shrinkage or with the film thickness. When the thickness of the non-heat-shrinkable film is less than 3 μm, the number of wrinkles becomes too large, cracks are easily generated between wrinkles and wrinkles, and the metallic luster is reduced, so the design is lacking, and the non-heat shrinkage When forming a metal thin film layer of a conductive film or coating a resin layer, wrinkles and the like are generated and workability deteriorates, which is not preferable. When the thickness of the non-heat-shrinkable film is larger than 12 μm, the number of wrinkles becomes too small, the film becomes brittle, and the design is poor. In addition, when the film is used for a cap seal, for example, the heat-shrinkable film and the non-heat-shrinkable film are peeled off from each other at the top portion, which is not preferable because a so-called erecting occurs. From the viewpoint of prevention of standing, the thickness of the non-heat-shrinkable film is more preferably from 3 to 9 μm, and most preferably from 3 to 6 μm.
【００１４】本発明の金属薄膜層は、真空蒸着、スパッ
タリング、イオンプレーティング等の従来公知の方法
で、非熱収縮性フイルム上に形成できる。金属薄膜層の
材料としては、アルミニウム、クロム、ニッケル、ス
ズ、銀、その他の金属、又は合金何れからなるものであ
ってもよい。The metal thin film layer of the present invention can be formed on a non-heat-shrinkable film by a conventionally known method such as vacuum deposition, sputtering, or ion plating. As the material of the metal thin film layer, any of aluminum, chromium, nickel, tin, silver, other metals, and alloys may be used.
【００１５】非熱収縮性フイルムと金属薄膜層との密着
力に影響を与えない範囲で、非熱収縮性フイルムと金属
薄膜層との間に樹脂層を設けてもよい。樹脂層の樹脂と
しては、非熱収縮性フイルムと金属薄膜層の両方に密着
し、かつ金属蒸着等の適性があればよく、例えば、ポリ
エステル、アクリル、メラミン、フェノール、塩化ビニ
ル、エポキシ等の樹脂が使用できる。上記の樹脂は、熱
可塑性、熱硬化性、何れであっても特に問題はないが、
金属薄膜層形成時や熱収縮時の耐熱性を考慮すれば、熱
硬化性樹脂を使用すればより万全である。また、樹脂層
には、着色を目的に染料や顔料を添加することができ、
染料や顔料の種類を選択することにより所望の色の熱収
縮性包装用フイルムを得ることができる。染料や顔料の
添加量は、密着性に影響を与えない範囲で、使用する樹
脂の種類により適宜決定すればよい。A resin layer may be provided between the non-heat-shrinkable film and the metal thin-film layer as long as it does not affect the adhesion between the non-heat-shrinkable film and the metal thin-film layer. As the resin of the resin layer, it is sufficient that the resin layer is in close contact with both the non-heat-shrinkable film and the metal thin film layer and has a suitable property such as metal vapor deposition, for example, a resin such as polyester, acrylic, melamine, phenol, vinyl chloride, and epoxy. Can be used. The above resin, thermoplastic, thermosetting, there is no particular problem in any,
In consideration of the heat resistance during the formation of the metal thin film layer and the heat shrinkage, the use of a thermosetting resin is more thorough. In addition, a dye or pigment can be added to the resin layer for the purpose of coloring,
By selecting the type of dye or pigment, a heat-shrinkable packaging film of a desired color can be obtained. The amount of the dye or pigment to be added may be appropriately determined depending on the type of the resin to be used within a range that does not affect the adhesion.
【００１６】本発明に使用する厚さ０．５〜５μｍの粘
着層は、熱収縮性フイルムと、非熱収縮性フイルムに設
けた金属薄膜層との間に全面に形成する。粘着層を形成
する粘着剤は、粘着層の厚さが０．５〜５μｍで熱収縮
性フイルムと非熱収縮性フイルムの密着強度が常温で１
０〜５００ｇ／１５ｍｍである条件を満足するものであ
れば特に制限はない。例えば、アクリル、ウレタン、ゴ
ム系、その他市販の粘着剤が使用できる。熱収縮性フイ
ルムと非熱収縮性フイルムの密着強度は、常温で１０〜
５００ｇ／１５ｍｍとなるように、粘着層の厚さ、及び
粘着層を形成する粘着剤の種類を適宜調整すればよい。
本発明の熱収縮性包装用フイルムは、熱収縮性フイルム
と非熱収縮性フイルムの密着強度を常温で１０〜５００
ｇ／１５ｍｍとしたので、熱収縮時に粘着層自身のず
れ、粘着層と熱収縮性フイルムとの貼り合わせ面のず
れ、又は粘着層と金属薄膜層との貼り合わせ面のずれが
適度に大きいので、熱収縮性包装用フイルムの収縮を阻
害せず、収縮が十分に行われる。また、収縮により現出
するしわも、立体的で、かつランダムな形状で、全体に
満遍なく現出し、意匠性に富んだものとなる。粘着層
は、加熱による温度上昇により柔らかくなるので、熱収
縮性フイルムと非熱収縮性フイルム間の密着強度は低下
するが、常温の密着強度が１０〜５００ｇ／１５ｍｍの
範囲内であれば、熱収縮性包装用フイルムの性能に影響
を与えない。熱収縮性フイルムと非熱収縮性フイルムの
密着強度が１０ｇ／１５ｍｍより小さいと、熱収縮性包
装用フイルムの加工時や経時で熱収縮性フイルムと非熱
収縮性フイルムが容易に剥離してしまい、例えば、キャ
ップシールに使用した場合には、スリット工程、センタ
ーシール行程での剥離や熱収縮時の天立ちが発生するの
で好ましくない。熱収縮性フイルムと非熱収縮性フイル
ムの密着強度が５００ｇ／１５ｍｍより大きいと、熱収
縮時に、粘着層自身のずれ、粘着層と熱収縮性フイルム
との貼り合わせ面のずれ、又は粘着層と金属薄膜層との
貼り合わせ面のずれが小さくなるので、熱収縮性包装用
フイルムの収縮を阻害してしまい、収縮が不十分になっ
たり、収縮に要する時間が長くなったりするので好まし
くない。また、収縮により現出するしわも、密着強度が
強いために、全体に満遍なくしわが現出せずに局部的に
大きなしわや非熱収縮性フイルムの剥離によるうきが発
生したり、場合によっては非熱収縮性フイルムが破れた
りする問題があり、意匠性にも欠けるので好ましくな
い。従って、熱収縮性フイルムと非熱収縮性フイルムの
密着強度は１０〜５００ｇ／１５ｍｍであれば問題はな
いが、上記欠点の防止の観点から２０〜３００ｇ／１５
ｍｍがより好ましく、特に３０〜２００ｇ／１５ｍｍが
最も好ましい。The adhesive layer having a thickness of 0.5 to 5 μm used in the present invention is formed on the entire surface between the heat-shrinkable film and the metal thin film layer provided on the non-heat-shrinkable film. The pressure-sensitive adhesive forming the pressure-sensitive adhesive layer has a thickness of 0.5 to 5 μm and an adhesive strength between the heat-shrinkable film and the non-heat-shrinkable film of 1 at room temperature.
There is no particular limitation as long as the condition of 0 to 500 g / 15 mm is satisfied. For example, acrylic, urethane, rubber, and other commercially available adhesives can be used. The adhesive strength between the heat-shrinkable film and the non-heat-shrinkable film is 10 to 10 at room temperature.
The thickness of the pressure-sensitive adhesive layer and the type of the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer may be appropriately adjusted so as to be 500 g / 15 mm.
The heat-shrinkable film for packaging according to the present invention has an adhesive strength between the heat-shrinkable film and the non-heat-shrinkable film at room temperature of 10 to 500.
g / 15 mm, the displacement of the adhesive layer itself during heat shrinkage, the displacement of the bonding surface between the adhesive layer and the heat-shrinkable film, or the displacement of the bonding surface between the adhesive layer and the metal thin film layer are appropriately large. The shrinkage of the heat shrinkable packaging film is sufficiently prevented without inhibiting the shrinkage. Also, wrinkles that appear due to shrinkage appear three-dimensionally and in a random shape, evenly over the whole, and are rich in design. Since the pressure-sensitive adhesive layer is softened by the temperature rise due to heating, the adhesive strength between the heat-shrinkable film and the non-heat-shrinkable film decreases, but if the adhesive strength at room temperature is within the range of 10 to 500 g / 15 mm, Does not affect the performance of the shrinkable packaging film. If the adhesive strength between the heat-shrinkable film and the non-heat-shrinkable film is less than 10 g / 15 mm, the heat-shrinkable film and the non-heat-shrinkable film are easily peeled off during processing of the heat-shrinkable packaging film or over time. For example, when used for a cap seal, peeling in a slit process and a center sealing process and erecting during heat shrinkage are not preferable. If the adhesive strength between the heat-shrinkable film and the non-heat-shrinkable film is larger than 500 g / 15 mm, the heat-shrinkable film causes a shift in the adhesive layer itself, a shift in the bonding surface between the adhesive layer and the heat-shrinkable film, or a change in the pressure-sensitive adhesive layer. Since the displacement of the bonding surface with the metal thin film layer becomes small, the shrinkage of the heat-shrinkable packaging film is hindered, so that the shrinkage becomes insufficient or the time required for the shrinkage becomes long, which is not preferable. Also, wrinkles that appear due to shrinkage, due to the strong adhesion strength, wrinkles do not appear evenly over the whole, and locally large wrinkles or wrinkles due to peeling of the non-heat-shrinkable film occur, and in some cases, non-wrinkles There is a problem that the heat-shrinkable film is broken, and the design property is also poor. Therefore, there is no problem if the adhesive strength between the heat-shrinkable film and the non-heat-shrinkable film is 10 to 500 g / 15 mm, but from the viewpoint of preventing the above-mentioned defects, it is 20 to 300 g / 15.
mm is more preferable, and especially 30 to 200 g / 15 mm is most preferable.
【００１７】粘着層を形成する方法は、グラビアコート
法、リバースコート法、バーコート法、ダイコート法
等、従来公知のコーティング方法で形成できる。The adhesive layer can be formed by a conventionally known coating method such as a gravure coating method, a reverse coating method, a bar coating method, and a die coating method.
【００１８】粘着層の厚さは、０．５〜５μｍが好まし
い。粘着層の厚さが、０．５μｍより薄いと熱収縮性フ
イルムと非熱収縮性フイルムが剥離したり、収縮により
現出するしわも、全体に満遍なくしわが現出せずに局部
的に大きなしわが発生し、意匠性に欠けるので好ましく
ない。また、キャップシールに使用した場合には、収縮
により天立ちが発生し易くなるので好ましくない。粘着
層の厚さが、５μｍより厚いと粘着層が経時で熱収縮性
包装用フイルムの断面からはみ出して、ブロッキングが
発生するので好ましくない。熱収縮性包装用フイルムを
センターシールによりチューブ状にした後、裁断したも
のを重ねたり、裁断後予備成形したものを重ねたりする
とブロッキングが発生するので好ましくない。特に、熱
収縮性包装用フイルムをスリット工程後やセンターシー
ル工程後にチューブ状のものをロール状態で保管してお
くと、次工程で熱収縮性包装用フイルムを巻き出す時
に、ブロッキングの発生により熱収縮性包装用フイルム
が破れたり、切れたりするので好ましくない。従って、
粘着層の厚さは、０．５〜５μｍ、より万全を期せば
１．５〜４μｍがより好ましい。The thickness of the adhesive layer is preferably 0.5 to 5 μm. If the thickness of the adhesive layer is less than 0.5 μm, the heat-shrinkable film and the non-heat-shrinkable film are peeled off, and wrinkles that appear due to shrinkage are locally large without wrinkles appearing uniformly. It is not preferable because it causes wrinkles and lacks design properties. Further, when used for a cap seal, shrinkage tends to cause erection, which is not preferable. If the thickness of the pressure-sensitive adhesive layer is more than 5 μm, the pressure-sensitive adhesive layer protrudes from the cross-section of the heat-shrinkable packaging film with the passage of time, which is not preferable because blocking occurs. It is not preferable that the heat-shrinkable packaging film is formed into a tube shape by a center seal and then overlapped with the cut one, or overlapped with the preformed one after the cut, because blocking occurs. In particular, if the heat-shrinkable packaging film is stored in a roll state after the slitting step or the center sealing step, the heat-shrinkable packaging film is unwound due to blocking when unwinding the film in the next step. It is not preferable because the film for shrinkable packaging is torn or cut. Therefore,
The thickness of the adhesive layer is preferably 0.5 to 5 μm, and more preferably 1.5 to 4 μm for completeness.
【００１９】ここで、本発明に係る熱収縮性包装用フイ
ルムについて、図面を参照しながら説明する。図１は、
本発明に係る熱収縮性包装用フイルムの一例を示す一部
拡大断面図であり、熱収縮性フイルム１の片面に、粘着
層２、金属薄膜層３、非熱収縮性フイルム５が順次形成
されている。図２は、本発明に係る熱収縮性包装用フイ
ルムに樹脂層を形成した一例を示す一部拡大断面図であ
り、熱収縮性フイルム１の片面に、粘着層２、金属薄膜
層３、樹脂層４、非熱収縮性フイルム５が順次形成され
ている。Here, the heat shrinkable packaging film according to the present invention will be described with reference to the drawings. FIG.
1 is a partially enlarged cross-sectional view showing an example of a heat-shrinkable packaging film according to the present invention, in which an adhesive layer 2, a metal thin film layer 3, and a non-heat-shrinkable film 5 are sequentially formed on one surface of a heat-shrinkable film 1. ing. FIG. 2 is a partially enlarged sectional view showing an example in which a resin layer is formed on the heat-shrinkable packaging film according to the present invention, and an adhesive layer 2, a metal thin film layer 3, and a resin A layer 4 and a non-heat-shrinkable film 5 are sequentially formed.
【００２０】[0020]
【実施例１】厚さ６μｍのポリエチレンテレフタレート
フイルムの片面にポリエステル樹脂、硬化剤、染料を混
合した配合塗料（固形分約２０％）をグラビアコート法
でコーティング後、１４０℃で３０秒間乾燥して、厚さ
１μｍの樹脂層を形成し、さらに真空蒸着法でアルミニ
ウム薄膜層を約４００〜５００Åの厚さに形成して、ア
ルミニウム薄膜層を有する非熱収縮性フイルムを得た。
次に、熱収縮率が５０％以上である厚さ４０μｍの熱収
縮性塩化ビニルフイルム（三菱樹脂社製ヒシレックス５
０３）に粘着剤（日本合成化学工業社製コーポニール８
０２０）塗料（固形分約１５％）をグラビアコート法で
コーティング後、乾燥して厚さ３μｍの粘着層を形成し
たものを、アルミニウム薄膜層を有する非熱収縮性フイ
ルムのアルミニウム薄膜層側と貼り合わせて、ゴールド
色の金属光沢を有する熱収縮性包装用フイルムを得た。
得られた熱収縮性包装用フイルムの密着強度をＴ型剥離
試験にて測定したところ５０ｇ／１５ｍｍであった。EXAMPLE 1 A coating material (solid content: about 20%) in which a polyester resin, a curing agent, and a dye were mixed was coated on one side of a 6 μm thick polyethylene terephthalate film by a gravure coating method, and then dried at 140 ° C. for 30 seconds. Then, a resin layer having a thickness of 1 μm was formed, and an aluminum thin film layer was formed to a thickness of about 400 to 500 ° by a vacuum evaporation method to obtain a non-heat-shrinkable film having an aluminum thin film layer.
Next, a heat-shrinkable vinyl chloride film having a heat shrinkage of 50% or more and a thickness of 40 μm (Hishilex 5 manufactured by Mitsubishi Plastics, Inc.)
03) with an adhesive (COPONYL 8 manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)
020) A paint (solid content: about 15%) is coated by a gravure coating method, and then dried to form an adhesive layer having a thickness of 3 μm, and is adhered to the aluminum thin film layer side of the non-heat-shrinkable film having the aluminum thin film layer. In addition, a heat-shrinkable packaging film having a gold metallic luster was obtained.
The adhesive strength of the obtained heat-shrinkable packaging film was measured by a T-peel test to find that it was 50 g / 15 mm.
【００２１】[0021]
【実施例２】非熱収縮性フイルムの樹脂層が形成されて
いないこと以外は、実施例１と同様の方法で、シルバー
色の金属光沢を有する熱収縮性包装用フイルムを得た。
得られた熱収縮性包装用フイルムの密着強度をＴ型剥離
試験にて測定したところ５０ｇ／１５ｍｍであった。Example 2 A heat-shrinkable packaging film having a silver metallic luster was obtained in the same manner as in Example 1 except that the resin layer of the non-heat-shrinkable film was not formed.
The adhesive strength of the obtained heat-shrinkable packaging film was measured by a T-peel test to find that it was 50 g / 15 mm.
【００２２】[0022]
【比較例１】粘着層の厚さを８μｍにしたこと以外は、
実施例１と同様の方法でゴールド色の金属光沢を有する
熱収縮性包装用フイルムを得た。得られた熱収縮性包装
用フイルムの密着強度をＴ型剥離試験にて測定したとこ
ろ３００ｇ／１５ｍｍであった。Comparative Example 1 Except that the thickness of the adhesive layer was 8 μm,
A heat-shrinkable packaging film having a gold metallic luster was obtained in the same manner as in Example 1. The adhesive strength of the obtained heat-shrinkable packaging film was measured by a T-peel test to find that it was 300 g / 15 mm.
【００２３】[0023]
【比較例２】実施例１で使用した粘着剤の代わりに接着
剤（東洋モートン社製ＡＤ−５７７−１：ＡＤ−ＲＴ８
＝１０：１ 固形分３０％）を使用して、グラビアコー
ト法でコーティング後、乾燥して厚さ３μｍの接着層を
形成したこと以外は、実施例１と同様の方法でゴールド
色の金属光沢を有する熱収縮性包装用フイルムを得た。
得られた熱収縮性包装用フイルムの密着強度をＴ型剥離
試験にて測定したところ６００ｇ／１５ｍｍであった。Comparative Example 2 An adhesive (AD-577-1: AD-RT8 manufactured by Toyo Morton Co., Ltd.) was used instead of the pressure-sensitive adhesive used in Example 1.
= 10: 1 solid content 30%), and coated by a gravure coating method, followed by drying to form an adhesive layer having a thickness of 3 μm. Was obtained.
The adhesive strength of the obtained heat shrinkable packaging film was measured by a T-peel test to find that it was 600 g / 15 mm.
【００２４】[0024]
【比較例３】実施例２で使用した粘着剤の代わりに接着
剤（東洋モートン社製ＡＤ−５７７−１：ＡＤ−ＲＴ８
＝１０：１ 固形分３０％）を使用して、グラビアコー
ト法でコーティング後、乾燥して厚さ３μｍの接着層を
形成したこと以外は、実施例１と同様の方法でシルバー
色の金属光沢を有する熱収縮性包装用フイルムを得た。
得られた熱収縮性包装用フイルムは、非熱収縮性フイル
ムとアルミニウム薄膜層間で容易に剥離し、密着強度を
Ｔ型剥離試験にて測定したところ２ｇ／１５ｍｍであっ
た。Comparative Example 3 An adhesive (AD-577-1: AD-RT8 manufactured by Toyo Morton Co., Ltd.) was used instead of the pressure-sensitive adhesive used in Example 2.
= 10: 1 solid content 30%), and coated by a gravure coating method, and then dried to form an adhesive layer having a thickness of 3 μm, except that a silver-colored metallic luster was formed in the same manner as in Example 1. Was obtained.
The obtained heat-shrinkable packaging film was easily peeled between the non-heat-shrinkable film and the aluminum thin film layer, and the adhesion strength was 2 g / 15 mm as measured by a T-type peel test.
【００２５】実施例１、２、及び比較例１〜３の熱収縮
性包装用フイルムをそれぞれセンターシール加工してチ
ューブ状とし、最大口径２８．５ｍｍであるコカコーラ
レギュラーサイズの瓶を使用して下記の条件にてキャッ
プシールとしての性能を比較した。結果を表に示す。ま
た、実施例１、及び２の熱収縮性包装用フイルムをセン
ターシール加工してチューブ状としたものを、ロール状
態のままでキャップシール自動機を使用して瓶に装填し
たところスムーズに装填できた。The heat-shrinkable packaging films of Examples 1 and 2 and Comparative Examples 1 to 3 were each formed into a tube by center-sealing and using a regular Coca-Cola bottle having a maximum diameter of 28.5 mm. The performance as a cap seal was compared under the following conditions. The results are shown in the table. In addition, the heat-shrinkable packaging films of Examples 1 and 2 were formed into a tube by center sealing and then loaded into a bottle using a cap-seal automatic machine in a rolled state. Was.
【００２６】１．熱収縮条件 使用機械 国際電機ハイエーストンネル 温度及び時間 ２００℃×１０秒 収縮率 ２０％1. Heat shrinking conditions Machine used Kokusai Electric Hiace Tunnel Temperature and time 200 ° C x 10 seconds Shrinkage 20%
【００２７】２．熱収縮適性 １の条件で、瓶に適合して確実に熱収縮したものを○、
瓶に密着性よく熱収縮しないものを×として評価した。2. Heat shrink suitability Under the conditions of 1, the heat shrink that conformed to the bottle and was surely heat shrunk
Those that did not thermally shrink with good adhesion to the bottle were evaluated as x.
【００２８】３．しわ １の条件で熱収縮後、しわがキャップシール全体に満遍
なく現出したものを○、局部的で、満遍なく現出しなか
ったものを×とした。3. Wrinkles After thermal shrinkage under the condition of 1, the wrinkles uniformly appeared on the entire cap seal were evaluated as ○, and those that were localized and did not uniformly appear were evaluated as ×.
【００２９】４．うき １の条件で熱収縮後、非熱収縮性フイルムが剥離して、
うきあがらなかったものを○、うきあがったものを×と
した。4. After heat shrinking under the conditions of 1, the non-heat shrinkable film peels off,
Those that did not clear were rated as O, and those that lifted were rated X.
【００３０】５．天立ち １の条件で熱収縮後、天部において、非熱収縮性フイル
ムが剥離して、うきあがらなかったものを○、うきあが
ったものを×とした。5. After heat shrinking under the condition of 1, the non-heat-shrinkable film was peeled off at the top portion and was not raised, and was evaluated as x.
【００３１】６．ブロッキング センターシール加工後のチューブ状のものをロール状態
で１０日間放置して、ブロッキングが発生したものを
○、発生しなかったものを×とした。6. Blocking The tube-shaped one after the center seal processing was left in a roll state for 10 days, and the case where blocking occurred was evaluated as ○, and the case where blocking did not occur was evaluated as ×.
【００３２】[0032]
【表】 【table】
【００３３】表に示されている通り、本発明である実施
例１、及び２の熱収縮性包装用フイルムは、熱収縮性塩
化ビニルフイルムと非熱収縮性フイルムの密着強度が５
０ｇ／１５ｍｍと弱いので、キャップシールに使用した
場合には、熱収縮性を阻害されず、全体に満遍なくしわ
が現出して、剥離によるうきや天立ちもなく、またブロ
ッキングも発生しなかった。従って、予備成形用のキャ
ップシールとして使用しても全く問題なく、また自動機
装填用のキャップシールとしても十分に実用に耐えるも
のであった。しかし、比較例１から明らかなように、熱
収縮性塩化ビニルフイルムと非熱収縮性フイルムの密着
強度が３００ｇ／１５ｍｍであり、１０〜５００ｇ／１
５ｍｍの範囲内であっても、粘着層の厚さが８μｍと厚
いとブロッキングが発生した。また、比較例２から明ら
かなように、接着層の厚さが３μｍであり、１〜５μｍ
の範囲内であっても、熱収縮性塩化ビニルフイルムと非
熱収縮性フイルムの密着強度が６００ｇ／１５ｍｍと強
いと、熱収縮性が阻害されて、局部的にしわが現出し
て、うきも発生した。さらに、比較例３から明らかなよ
うに、接着層の厚さが３μｍであり、１〜５μｍの範囲
内であっても、熱収縮性塩化ビニルフイルムと非熱収縮
性フイルムの密着強度が２ｇ／１５ｍｍと非常に弱い
と、熱収縮時に熱収縮性塩化ビニルフイルムと非熱収縮
性フイルムとが容易に剥離して、しわ、うきや天立ちが
発生した。以上のように、比較例１〜３の熱収縮性包装
用フイルムは、キャップシールとして、実用に耐えるも
のではない。As shown in the table, the heat-shrinkable packaging films of Examples 1 and 2 of the present invention have an adhesive strength of 5 between the heat-shrinkable vinyl chloride film and the non-heat-shrinkable film.
Since it was as weak as 0 g / 15 mm, when it was used for a cap seal, heat shrinkage was not hindered, wrinkles appeared evenly on the whole, and there was no peeling, no standing, and no blocking. Therefore, there was no problem in using it as a cap seal for preforming, and it was sufficiently practical for use as a cap seal for automatic machine loading. However, as is apparent from Comparative Example 1, the adhesive strength between the heat-shrinkable vinyl chloride film and the non-heat-shrinkable film was 300 g / 15 mm, and 10 to 500 g / 1.
Even in the range of 5 mm, blocking occurred when the thickness of the adhesive layer was as large as 8 μm. Further, as is apparent from Comparative Example 2, the thickness of the adhesive layer was 3 μm,
When the adhesive strength between the heat-shrinkable vinyl chloride film and the non-heat-shrinkable film is as strong as 600 g / 15 mm, the heat shrinkage is hindered, wrinkles appear locally, and wrinkles occur. did. Further, as is apparent from Comparative Example 3, even when the thickness of the adhesive layer is 3 μm and the thickness is in the range of 1 to 5 μm, the adhesive strength between the heat-shrinkable vinyl chloride film and the non-heat-shrinkable film is 2 g / m. When it was very weak, 15 mm, the heat-shrinkable vinyl chloride film and the non-heat-shrinkable film were easily peeled off during heat shrinkage, and wrinkles, wrinkles and erections occurred. As described above, the heat-shrinkable packaging films of Comparative Examples 1 to 3 are not practically usable as cap seals.
【００３４】[0034]
【発明の効果】（１）本発明の熱収縮性包装用フイルム
は、熱収縮すると全体に満遍なくしわが現出するが、し
わとしわの間にクラックが発生しないので優れた金属光
沢を有する。 （２）本発明の熱収縮性包装用フイルムは、非熱収縮性
フイルムが外側に存在するので、熱収縮により現出する
しわが非常に立体的である。 （３）本発明の熱収縮性包装用フイルムは、熱収縮性フ
イルムと、金属薄膜層を形成した非熱収縮性フイルムと
を金属薄膜層を内側にして、厚さ０．５〜５μｍの粘着
層で全面に貼り合わせてあり、熱収縮性フイルムと非熱
収縮性フイルムの密着強度が１０〜５００ｇ／１５ｍｍ
となるように、粘着層を調整した。熱収縮性フイルムと
非熱収縮性フイルムの密着強度が１０〜５００ｇ／１５
ｍｍと弱いので、熱収縮時に、粘着層自身のずれ、粘着
層と熱収縮性フイルムとの貼り合わせ面のずれ、又は粘
着層と金属薄膜層との貼り合わせ面のずれが適度に大き
いので、熱収縮性包装用フイルムの収縮を阻害せず、収
縮が十分に行われ、収縮に要する時間も短くてすむ。ま
た、収縮により現出するしわも、密着強度が弱いため
に、立体的で、かつランダムな形状で、全体に満遍なく
現出し、局部的に大きなしわや非熱収縮性フイルムの剥
離によるうきが発生したり、場合によっては非熱収縮性
フイルムが破れたりすることもなく、意匠性にも富んで
いる。従って、収縮率が大きくなっても現出するしわに
は特に影響がなく、例えば熱収縮性包装用フイルムを一
升瓶のキャップシールとして使用した場合でも、低収縮
の胴部と高収縮の口部とで現出するしわに差異はなく、
何れも立体的で、かつランダムな形状で、全体に満遍な
くしわが現出するので意匠性にも富んでいる。また、し
わとしわの間にはクラックが生じないので、金属光沢は
収縮の後でも低下しない。 （４）本発明の熱収縮性包装用フイルムは、粘着層が厚
さ０．５〜５μｍと薄いので、粘着層が経時で熱収縮性
包装用フイルムの断面からはみ出して、所謂ブロッキン
グが発生することもない。従って、本発明の熱収縮性包
装用フイルムをセンターシールによりチューブ状にした
後、裁断したものを重ねたり、裁断後予備成形したもの
を重ねてもブロッキングにより離れなくなる問題はな
い。特に、熱収縮性包装用フイルムをスリット工程後や
センターシール工程後にチューブ状のものをロール状態
で保管しておいても、次工程で熱収縮性包装用フイルム
を巻き出す時に、ブロッキングの発生により熱収縮性包
装用フイルムが破れたり、切れたりする問題もなく保存
安定性が非常に向上した。従って、予備成形用のキャッ
プシールはもちろん、ロール状態での保管が必要な自動
機装填用のキャップシール等にも、使用可能となった。 （５）金属薄膜層を設けた非熱収縮性フイルムは、金属
薄膜層面が熱収縮性フイルムと貼り合わされており、金
属薄膜層が表層ではなく内側に存在するので、金属薄膜
層に容易に傷がついたり、経時で金属薄膜層が容易に腐
食したりする問題がない。さらに、熱収縮性フイルムと
非熱収縮性フイルムの密着強度が１０〜５００ｇ／１５
ｍｍと弱いので、金属薄膜層面を内側にして貼り合わせ
ても、金属薄膜層にストレスがかからないので、熱収縮
性包装用フイルムの熱収縮時や製造時に金属薄膜層と非
熱収縮性フイルムの間で容易に剥離が生じるという問題
もない。以上のように、本発明の熱収縮性包装用フイル
ムは、十分に実用に耐えるものである。(1) The heat-shrinkable packaging film of the present invention shows an overall wrinkle when heat shrunk, but has excellent metallic luster because cracks do not occur between the wrinkles. (2) In the heat-shrinkable packaging film of the present invention, since the non-heat-shrinkable film exists on the outside, wrinkles appearing due to heat shrinkage are very three-dimensional. (3) The heat-shrinkable packaging film of the present invention comprises a heat-shrinkable film and a non-heat-shrinkable film on which a metal thin film layer is formed, with the metal thin film layer inside, and an adhesive having a thickness of 0.5 to 5 μm. The heat-shrinkable film and the non-heat-shrinkable film have an adhesion strength of 10 to 500 g / 15 mm.
The adhesive layer was adjusted so that Adhesion strength between heat-shrinkable film and non-heat-shrinkable film is 10 to 500 g / 15
mm, the displacement of the adhesive layer itself during heat shrinkage, the displacement of the bonding surface between the adhesive layer and the heat-shrinkable film, or the displacement of the bonding surface between the adhesive layer and the metal thin film layer is moderately large. The shrinkage of the heat shrinkable packaging film is not hindered, the shrinkage is sufficiently performed, and the time required for shrinkage is short. In addition, wrinkles that appear due to shrinkage, due to the low adhesion strength, appear in a three-dimensional and random shape evenly throughout, causing large wrinkles locally and wrinkles due to peeling of non-heat-shrinkable film. In addition, the non-heat-shrinkable film is not broken, and the design is rich. Therefore, even if the shrinkage rate becomes large, there is no particular effect on the wrinkles that appear, and for example, even when the heat shrinkable packaging film is used as a cap seal for a single bottle, a low shrinkage trunk and a high shrinkage mouth are used. There is no difference in wrinkles that appear in
Each of them is three-dimensional and has a random shape, and has wrinkles appearing evenly throughout, so that it is rich in design. Further, since no crack occurs between wrinkles, the metallic luster does not decrease even after shrinkage. (4) Since the heat-shrinkable packaging film of the present invention has a thin adhesive layer having a thickness of 0.5 to 5 μm, the adhesive layer protrudes from the cross-section of the heat-shrinkable packaging film over time, so-called blocking occurs. Not even. Therefore, even if the heat-shrinkable packaging film of the present invention is formed into a tube shape by a center seal and then cut and stacked, or preformed after being cut and stacked, there is no problem that the heat-shrinkable packaging film is not separated due to blocking. In particular, even if the heat-shrinkable packaging film is stored in a rolled state after the slitting step or the center sealing step, when the heat-shrinkable packaging film is unwound in the next step, the film may be blocked. The storage stability was greatly improved without the problem of the heat shrinkable packaging film being broken or broken. Therefore, it can be used not only as a cap seal for preforming, but also as a cap seal for automatic machine loading which needs to be stored in a roll state. (5) In the non-heat-shrinkable film provided with the metal thin film layer, the surface of the metal thin film is bonded to the heat shrinkable film, and the metal thin film layer exists not on the surface but on the inside, so that the metal thin film layer is easily damaged. There is no problem that the metal thin film layer is easily corroded over time. Further, the adhesive strength between the heat-shrinkable film and the non-heat-shrinkable film is 10 to 500 g / 15.
mm, so that no stress is applied to the metal thin-film layer even when they are bonded together with the metal thin-film layer surface inside, so that the heat-shrinkable packaging film can be placed between the metal thin-film layer and the non-heat-shrinkable film during heat shrinkage or production. Therefore, there is no problem that separation easily occurs. As described above, the heat-shrinkable packaging film of the present invention sufficiently withstands practical use.
【図１】本発明に係る熱収縮性包装用フイルムの一例を
示す一部拡大断面図である。FIG. 1 is a partially enlarged sectional view showing an example of a heat-shrinkable packaging film according to the present invention.
【図２】本発明に係る熱収縮性包装用フイルムに樹脂層
を形成した一例を示す一部拡大断面図である。FIG. 2 is a partially enlarged sectional view showing an example in which a resin layer is formed on the heat-shrinkable packaging film according to the present invention.
１ 熱収縮性フイルム ２ 粘着層 ３ 金属薄膜層 ４ 樹脂層 ５ 非熱収縮性フイルム DESCRIPTION OF SYMBOLS 1 Heat-shrinkable film 2 Adhesive layer 3 Metal thin film layer 4 Resin layer 5 Non-heat-shrinkable film
Claims (3)
非熱収縮性フイルムを順次積層してなるものであって、
熱収縮性フイルムと金属薄膜層を設けた非熱収縮性フイ
ルムとを金属薄膜層を内側にして厚さ０．５〜５μｍの
粘着層で全面に貼り合わせたこと、及び熱収縮性フイル
ムと非熱収縮性フイルムとの密着強度が１０〜５００ｇ
／１５ｍｍであることを特徴とする熱収縮性包装用フイ
ルム。1. A heat-shrinkable film, an adhesive layer, a metal thin film layer,
Non-heat-shrinkable film is sequentially laminated,
A heat-shrinkable film and a non-heat-shrinkable film provided with a metal thin-film layer are stuck together with an adhesive layer having a thickness of 0.5 to 5 μm with the metal thin-film layer inside; Adhesion strength with heat shrinkable film is 10-500g
/ 15 mm, a heat-shrinkable packaging film.
樹脂層を形成してなる請求項１記載の熱収縮性包装用フ
イルム。2. The heat-shrinkable packaging film according to claim 1, wherein a resin layer is formed between the metal thin film layer and the non-heat-shrinkable film.
であり、かつ非熱収縮性フイルムの厚さが３〜１２μｍ
である請求項１又は２に記載の熱収縮性包装用フイル
ム。3. The heat-shrinkable film has a thickness of 30 to 70 μm.
And the thickness of the non-heat-shrinkable film is 3 to 12 μm.
The heat-shrinkable packaging film according to claim 1 or 2, wherein
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30742499A JP3168201B2 (en) | 1999-09-21 | 1999-09-21 | Heat shrinkable packaging film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30742499A JP3168201B2 (en) | 1999-09-21 | 1999-09-21 | Heat shrinkable packaging film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001088237A JP2001088237A (en) | 2001-04-03 |
| JP3168201B2 true JP3168201B2 (en) | 2001-05-21 |
Family
ID=17968903
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30742499A Expired - Lifetime JP3168201B2 (en) | 1999-09-21 | 1999-09-21 | Heat shrinkable packaging film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3168201B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4948212B2 (en) * | 2006-03-15 | 2012-06-06 | 株式会社きもと | Heat shrinkable film |
| CN102815049B (en) * | 2012-08-16 | 2015-02-25 | 深圳叶氏启恒印刷科技有限公司 | Heat-shrinkable thin film and preparation method thereof |
| WO2018232185A1 (en) * | 2017-06-14 | 2018-12-20 | Flir Commercial Systems, Inc. | Lens systems and methods of manufacture |
-
1999
- 1999-09-21 JP JP30742499A patent/JP3168201B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2001088237A (en) | 2001-04-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR0173474B1 (en) | Manufacturing method of laminated packaging material | |
| EP0578750B1 (en) | Stable pressure sensitive shrink label technique | |
| GB2184672A (en) | Packaging materials | |
| JPS62294542A (en) | Delaminate-resistant multilayer metal/polymer composite article | |
| JPH0661830B2 (en) | How to make a labeled hollow container | |
| EP1503898B1 (en) | Metallized high barrier lap-sealable liner for spiral wounds containers | |
| JP3168201B2 (en) | Heat shrinkable packaging film | |
| EP0189868B1 (en) | Packaging material and sealing cap | |
| JP4865938B2 (en) | Insulated container | |
| JP2003058057A (en) | Label for manganese dry battery and method for manufacturing manganese dry battery | |
| JP5055673B2 (en) | Heat shrinkable adhesive film | |
| JPH0628936B2 (en) | Heat-shrinkable sheet with excellent metallic luster | |
| JP4177986B2 (en) | Batteries covered with labels and label mounting method | |
| EP0841709B1 (en) | Protection and decoration label, especially for electric battery | |
| EP4025422B1 (en) | Metallized biaxially oriented polypropylene (bopp) film structure | |
| JPH1071663A (en) | Gas barrier laminate structure | |
| JP4655703B2 (en) | Easy peelable film and lid | |
| KR100419193B1 (en) | Battery | |
| JP2001272915A (en) | Heat shrinkable label | |
| JPH04279315A (en) | Manufacture of vessel with label | |
| JP7088128B2 (en) | Sealing material for tube containers and tube containers | |
| JP3877315B2 (en) | Heat shrinkable packaging film | |
| EP1124214A1 (en) | Heat-sensitive adhesive label, method of attaching the label, and dry cell attached with the label | |
| JPH058318A (en) | Method for manufacturing laminated packaging material | |
| JPH08244157A (en) | Gas barrier laminate containing paper |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| TRDD | Decision of grant or rejection written | ||
| R150 | Certificate of patent or registration of utility model |
Ref document number: 3168201 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080309 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090309 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090309 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100309 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100309 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110309 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120309 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120309 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130309 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140309 Year of fee payment: 13 |
|
| EXPY | Cancellation because of completion of term |