JPH0768363B2 - Heat-sealing film for packaging materials - Google Patents
Heat-sealing film for packaging materialsInfo
- Publication number
- JPH0768363B2 JPH0768363B2 JP5339588A JP5339588A JPH0768363B2 JP H0768363 B2 JPH0768363 B2 JP H0768363B2 JP 5339588 A JP5339588 A JP 5339588A JP 5339588 A JP5339588 A JP 5339588A JP H0768363 B2 JPH0768363 B2 JP H0768363B2
- Authority
- JP
- Japan
- Prior art keywords
- heat
- packaging
- sealing
- sealing film
- 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.)
- Expired - Lifetime
Links
- 238000007789 sealing Methods 0.000 title claims description 97
- 239000005022 packaging material Substances 0.000 title claims description 27
- 229920001577 copolymer Polymers 0.000 claims description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 16
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 13
- 238000000465 moulding Methods 0.000 claims description 10
- 229920001903 high density polyethylene Polymers 0.000 claims description 8
- 239000004700 high-density polyethylene Substances 0.000 claims description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- 229920002959 polymer blend Polymers 0.000 claims description 2
- 238000004806 packaging method and process Methods 0.000 description 69
- 239000000463 material Substances 0.000 description 62
- 229920005989 resin Polymers 0.000 description 35
- 239000011347 resin Substances 0.000 description 35
- -1 polypropylene Polymers 0.000 description 31
- 239000011888 foil Substances 0.000 description 25
- 238000000034 method Methods 0.000 description 24
- 229910052782 aluminium Inorganic materials 0.000 description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 23
- 239000000203 mixture Substances 0.000 description 23
- 239000004743 Polypropylene Substances 0.000 description 21
- 229920001155 polypropylene Polymers 0.000 description 21
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 16
- 239000000123 paper Substances 0.000 description 15
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 15
- 239000005038 ethylene vinyl acetate Substances 0.000 description 13
- 239000012945 sealing adhesive Substances 0.000 description 13
- 239000002775 capsule Substances 0.000 description 12
- 239000002985 plastic film Substances 0.000 description 12
- 239000010902 straw Substances 0.000 description 12
- 239000000758 substrate Substances 0.000 description 12
- 239000010410 layer Substances 0.000 description 11
- 239000000853 adhesive Substances 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 229920006255 plastic film Polymers 0.000 description 8
- 239000011086 glassine Substances 0.000 description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 238000010030 laminating Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000011111 cardboard Substances 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000009820 dry lamination Methods 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 239000002655 kraft paper Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- CMBGUBFZPOABLS-UHFFFAOYSA-N [Na].C=CCCCC Chemical compound [Na].C=CCCCC CMBGUBFZPOABLS-UHFFFAOYSA-N 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002991 molded plastic Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は包装用材料として有用な熱封緘性フィルムに関
するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a heat-sealing film useful as a packaging material.
更に詳しくは、シール袋やストリップ包装のように包装
袋を引裂くことによって内容物を取り出す形式の包装、
PTP（Press Through Pack）包装のように容器底部を指
頭で圧迫することによりアルミニゥム箔等の蓋材を破裂
させて内容物を取り出す形式の包装、あるいは果汁等を
充填したアルミニゥム箔製パウチや破砕し易いプラスチ
ックフィルム等を張った小窓を包装体壁の一部に設けた
ブリック型紙容器等のように包装体の特定の個所にスト
ローを突き刺して破り、内容物を吸い出す形式の包装な
ど、開封に際して包装体の少なくとも一部を破壊するこ
とによって内容物を取り出す形式の包装体用の基材に設
けう熱封緘性接着剤層として優れた物性を示す包装材用
熱封緘世フィルムを提供するものである。More specifically, a type of packaging in which the contents are taken out by tearing the packaging bag, such as a seal bag or strip packaging,
As in PTP (Press Through Pack) packaging, the bottom of the container is squeezed with your fingertips to rupture the lid material such as aluminum foil and take out the contents, or an aluminum foil pouch filled with fruit juice or crushed. When opening the packaging, such as a brick-shaped paper container that has a small window with an easy-to-use plastic film on it, pierces it with a straw at a specific point on the packaging and breaks it to suck out the contents. To provide a heat-sealing film for a packaging material, which has excellent physical properties as a heat-sealing adhesive layer provided on a base material for a packaging body in which the contents are taken out by breaking at least a part of the packaging body. is there.
（従来の技術） 医薬品、食品、機械・電子部品等の包装に適用される固
装形態として、シール袋、スティック包装、ピロー包
装、ストリップ包装、ブリスター包装、PTP包装、ブリ
ッ型容器等のように開封時に包装体壁の破壊を前提とす
る一群がある。そして、これらの包装体用基材にはアル
ミニゥム箔、ステンレス鋼箔等の金属箔、模造紙、上質
紙、グラシン紙等の用紙類あるいは種々のプラスチック
フィルム類の単独または二種以上の積層体が使用されて
いる。包装体を形成するには、同一の包装体用基材同志
あるいは異種の包装体用基材類を組み合わせて接着させ
ることにより組み立てられるが、通常、接着手段として
は塗布あるいは積層の方法によって包装体用基材の全面
または一部に設けられた熱封緘性接着材層の任意の部分
を熱封緘することで遂行されている。(Prior art) As a fixed form applied to packaging of pharmaceuticals, foods, machinery / electronic parts, etc., such as seal bags, stick packaging, pillow packaging, strip packaging, blister packaging, PTP packaging, brittle containers, etc. There is a group that presupposes the destruction of the package wall when opening. The base material for these packages may be aluminum foil, metal foil such as stainless steel foil, paper such as imitation paper, fine paper, glassine paper or various plastic films, or a laminate of two or more kinds. It is used. In order to form a package, the same packaging base material or different types of packaging base materials are assembled and bonded together. Usually, the bonding means is a coating or laminating method. This is accomplished by heat-sealing any part of the heat-sealing adhesive layer provided on the entire surface or a part of the base material for heat treatment.
前記の包装体用基材に設けられる熱封緘性の接着剤層は
従来、熱可塑性の樹脂組成物または塗料を塗布すること
により数μ程度の厚さの熱封緘性接着剤層としている。The heat-sealing adhesive layer provided on the above-mentioned base material for a package has heretofore been formed as a heat-sealing adhesive layer having a thickness of about several μm by applying a thermoplastic resin composition or paint.
しかし、近年になって熱封緘強度の向上や包装品質の安
定化のために、また特にブリスター包装やPTP包装にお
いては熱封緘後のカール性の改良のために熱封緘性のあ
る熱可塑性樹脂フィルムを包装用基材類に融着させる
か、あるいは接着剤を介して粘着することにより熱封緘
性接着剤層とした複合基材を使用する方法が行なわれる
ようになって来ており、ポリエチレンやポリプロピレン
等のポリオレフィン、エチレンやプロピレン等のオレフ
ィン相互の共重合体あるいは、それらのオレフィン類と
他のα−オレフィン類、例えばブテン−１、ヘキセン−
１、４−メチルペンテン−１、オクテン−１等との共重
合体、エチレン−（メタ）アクリル酸共重合体等のカル
ボキシル基を有する重合体類の金属塩のように、ナトリ
ウムイオンまたは亜鉛イオンのような一価或いは多価の
金属イオンと共に構成されたアイオノマー、塩化ビニリ
デン共重合体、ポリ酢酸ビニル、塩化ビニル−酢酸ビニ
ル共重合体、エチレン−酢酸ビニル共重合体（EVA）等
の種々の（共）重合体のフィルム等が一般にその目的の
ための熱封緘性フィルムとして使用されている。However, in recent years, in order to improve the heat sealing strength and stabilize the packaging quality, and in particular for blister packaging and PTP packaging, to improve the curling property after heat sealing, a thermoplastic resin film having heat sealing property A method of using a composite substrate as a heat-sealing adhesive layer by fusing the above with a packaging substrate or by adhering it with an adhesive has been used. Polyolefins such as polypropylene, copolymers of olefins such as ethylene and propylene, or olefins thereof and other α-olefins such as butene-1, hexene-
Sodium ion or zinc ion such as a metal salt of a polymer having a carboxyl group such as a copolymer with 1,4-methylpentene-1, octene-1, etc., an ethylene- (meth) acrylic acid copolymer, etc. Various ionomers, vinylidene chloride copolymers, polyvinyl acetate, vinyl chloride-vinyl acetate copolymers, ethylene-vinyl acetate copolymers (EVA), etc. (Co) polymer films and the like are commonly used as heat-sealing films for that purpose.
（発明が解決しようとする問題点） 前記したように開封に際して包装体の少なくとも一部を
破壊することによって内容物を取り出す形式の包装体に
おいて、それぞれ用途により開封の方式が異るため基材
に設ける熱封緘性接着剤層を構成するための熱封緘性フ
ィルムには目的によって諸種の要件が求められる。(Problems to be Solved by the Invention) As described above, in a package of a type in which the contents are taken out by breaking at least a part of the package at the time of unsealing, the method of unsealing is different depending on the application, and thus the substrate is used. The heat-sealing film for forming the heat-sealing adhesive layer to be provided is required to have various requirements depending on the purpose.
例えば目的の包装体がシール袋、スティック包装、ピロ
ー包装、ストリップ包装、ブリスター包装等の場合には
開封袋を引裂くことにより行なわれるので包装用基材は
アルミニゥム箔、模造紙、グラシン紙、延伸処理や欠削
加工を施したポリプロピレンフィルムなど、引裂き性の
良好なものが使用されるが、熱封緘性接着剤を構成する
ための熱封緘性フィルムの熱封緘強度が十分に大きくな
ければならないのは当然であるが、その他に引裂き性が
良好でなければ引裂きによって包装袋が破断した時の衝
撃で内容物がこぼれたり、破断部分が不規則になるため
内容物の取り出しが円滑に行なわれていないなどの問題
が生じる。For example, when the target package is a seal bag, a stick package, a pillow package, a strip package, a blister package, etc., it is carried out by tearing an open bag, so that the packaging base material is aluminum foil, imitation paper, glassine paper, stretched paper. A good tearing property such as polypropylene film that has been subjected to treatment or chipping is used, but the heat sealing strength of the heat sealing film for constituting the heat sealing adhesive must be sufficiently large. Of course, if the tearability is not good, the contents can be taken out smoothly because the contents are spilled by the impact when the packaging bag is ruptured due to the tear and the ruptured parts are irregular. There is a problem such as no.
また、目的の包装体がブリスター包装やPTP包装のよう
な場合には包装形態が内容物を格納するための容器の部
分となるポケットを成形したプラスチックシートの加工
成形体と、蓋の部分となる包装体用基材との二つの部分
とからなり、容器はポリ塩化ビニルやポリプロピレン等
のプラスチックシートを成形したものが通常、使用さ
れ、蓋材にはアルミニゥム箔、グラシン紙、白ボール紙
等が使用されることが多く、蓋と容器とは蓋に設けられ
た接着剤層によって熱封緘されていて、開封は容器底部
を指頭で押圧するなど、蓋材を直接あるいは間接的に破
裂させることによっている。従って、蓋材となる基材に
積層する熱封緘性フィルムは蓋材の基材と容器の材質で
あるプラスチックに対して充分な熱封緘強度を示すとと
もに蓋材の基材の破裂性を低下させてはならない。When the target package is a blister package or PTP package, the packaging form is the molded part of the plastic sheet that forms the pocket that becomes the part of the container for storing the contents, and the part of the lid. It consists of two parts, a packaging base material and a container.Molded plastic sheets such as polyvinyl chloride and polypropylene are usually used for the container, and aluminum foil, glassine paper, white cardboard, etc. are used for the lid material. Often used, the lid and container are heat-sealed by an adhesive layer provided on the lid, and opening is performed by rupturing the lid material directly or indirectly, such as pressing the bottom of the container with a fingertip. There is. Therefore, the heat-sealing film laminated on the base material to be the lid material shows sufficient heat-sealing strength to the base material of the lid material and the plastic of the material of the container and reduces the rupture property of the base material of the lid material. must not.
果汁、スープ等主として液体の包装に使用されるブリッ
ク型容器等のように、例えば紙製の基材から構成された
容器壁に設けた小窓に張られたプラスチックフィルムや
アルミニゥム箔、紙等にストローを突き刺して破り、主
として液体の内容物を取り出す形式の容器において、小
窓を設けた紙製の基材と熱封緘性フィルムとを積層した
包装材用熱封緘性フィルムから構成し、熱封緘性フィル
ムを熱封緘性接着剤層とすると同時に取り出し口用封緘
フィルムとしても使用する場合には前記熱封緘性フィル
ムは取り扱い過程で破壊しない強度を有するとともに、
ストロー等で容易に突き破ることが出来ることが必要で
ある。For juice, soup, etc., such as brick-type containers used mainly for liquid packaging, for example, plastic films, aluminum foil, paper, etc. stretched on a small window provided on the wall of a container made of paper base material. In a container of a type in which a straw is pierced and ruptured to mainly take out liquid contents, the heat sealing film for packaging is formed by laminating a paper base material having a small window and a heat sealing film. When the heat-sealing adhesive film is used as the heat-sealing adhesive layer at the same time as the heat-sealing adhesive film, the heat-sealing film has strength not to be destroyed in the handling process,
It is necessary to be able to easily break through with a straw or the like.
以上のように破壊により開封を行なう包装形態にも各種
の方式や用途があるため、包装体用基材の熱封緘性接着
剤層とする熱封緘性フィルムにも本来の目的である熱封
緘性の他にそれぞれの破壊性を損なわないことが必要で
ある。As described above, there are various methods and applications for the packaging form that opens by destruction.Therefore, the heat sealing property that is the original purpose of the heat sealing film used as the heat sealing adhesive layer of the packaging base material is the original purpose. Besides, it is necessary not to impair the destructiveness of each.
しかしながら、包装形態によってそれぞれ包装材用熱封
緘性フィルムが使用されてはいるが、同一基材であって
も種々の方式や用途に従ってこれらの熱封緘性フィルム
は使い分けされており、非常に煩雑であり、適用を誤る
ことが中々避けられないのが現状である。However, although heat-sealing films for packaging materials are used depending on the packaging form, even with the same base material, these heat-sealing films are used properly according to various methods and applications, which is very complicated. However, the current situation is that mistakes in application are unavoidable.
（問題を解決するための手段） 本発明者等は開封に際して包装体の少なくとも一部を破
壊することによって内容物を取り出す形式の包装体用の
基材に設ける熱封緘性接着剤層として広範囲に使用する
ことができる包装材用熱封緘性フィルムとして、通常
の取扱いでは破損を生じない強度を有し、自己熱封緘
性のみならず、アルミニゥム箔等の金属基材、グラシン
紙、模造紙、白ボール紙等の紙類およびポリ塩化ビニ
ル、ポリエチレン、ポリプロピレン、ポリスチレン、ポ
リエチレンテレフタレート等の諸種のプラスチックフィ
ルムあるいはシート類など包装に使用される基材に対す
る熱封緘性が良好であり、易破裂性であって、例えば
PTP包装などにおいて蓋材として使用されるアルミニゥ
ム箔などに粘着して積層した場合にアウミニゥム箔の破
裂強度を余り大きくすることなく、容器底部の押圧によ
り簡単に破裂して内容物の取り出しが容易であり、易
引裂性であって、例えばクラフト紙に積層して包装用基
材としてシール袋とした包装体を引裂く時に、クラフト
紙の引裂き強度を余り高めたりせず、クラフト紙の裂け
る方向に沿って容易に引裂くことができ、ブリック包
装などの液体の取り出し口の封緘フィルムとして使用さ
れる場合にストローなどで突き破ることが容易であるよ
うな樹脂組成物の開発を目的として検討を行なって本発
明に到達したのである。(Means for Solving the Problem) The present inventors have extensively used as a heat-sealing adhesive layer provided on a base material for a package of a type in which the contents are taken out by breaking at least a part of the package when opening. As a heat-sealing film for packaging materials that can be used, it has strength that does not cause damage during normal handling, and it has not only self-sealing property but also metal base material such as aluminum foil, glassine paper, imitation paper, white Good heat sealability and easy rupture property for papers such as cardboard and various kinds of plastic films or sheets such as polyvinyl chloride, polyethylene, polypropylene, polystyrene, polyethylene terephthalate, etc. used for packaging. For example,
When laminated by sticking to aluminum foil, which is used as a lid material in PTP packaging, etc., the rupture strength of the aluminum foil does not increase too much, and it is easy to rupture by pressing the bottom of the container and the contents can be taken out easily. Yes, it is easily tearable, for example, when tearing a package that is laminated on kraft paper and used as a sealing bag as a packaging base material, does not increase the tear strength of kraft paper too much, Along with the aim of developing a resin composition that can be easily torn along, and is easy to break through with a straw or the like when used as a sealing film for a liquid outlet such as brick packaging The present invention has been reached.
即ち、本発明は少なくとも１種の、カルボキシル基を有
するエチレン・酢酸ビニル共重合体（Ａ）15〜50％（重
量％、以下すべて同様である）、少なくとも１種のスチ
レン（共）重合体（Ｂ）10〜60％および少なくとも１種
の高密度ポリエチレン（Ｃ）15〜40％［ただし、（Ａ）
＋（Ｂ）＋（Ｃ）＝100％である］からなる重合体混合
物（Ｄ）を成形してなる包装材用熱封緘性フィルムは、
実用上充分な強度を有し、自己熱封緘性および包装に使
用される前記のような各種基材類に対する熱封緘性が充
分に大きく、易破裂性、易引裂き性であるとともにスト
ロー挿入口等の封緘フィルムとして突き挿しの容易であ
るなどの諸特性を有することを見出して本願の発明を完
成したのである。That is, the present invention provides at least one kind of ethylene / vinyl acetate copolymer (A) having a carboxyl group (A) 15 to 50% (wt%, the same applies hereinafter) and at least one kind of styrene (co) polymer ( B) 10-60% and at least one high-density polyethylene (C) 15-40% [however, (A)
+ (B) + (C) = 100%], the heat-sealing film for a packaging material obtained by molding the polymer mixture (D)
It has practically sufficient strength, self-heat-sealing property and heat-sealing property for the above-mentioned various types of base materials used for packaging are sufficiently large, easy rupture property, easy tear property, and straw insertion port. The inventors of the present invention have completed the invention of the present application by discovering that it has various characteristics such as easy sealing and insertion as the sealing film.
また特に本発明の包装材用熱封緘性フィルムは更に熱封
緘を行なう際に発生するカールが著しく小さいことも見
出された。It was also found that the heat-sealing film for a packaging material according to the present invention has a remarkably small curl generated during heat-sealing.
本発明の包装材用熱封緘性フィルムを成形するための樹
脂混合物（Ｄ）の成分であるカルボキシル基を有するエ
チレン−酢酸ビニル共重合体（Ａ）としてはエチレン−
酢酸ビニル共重合体にカルボキシル基を化学的に結合し
た形で有するものが適当であり、その導入方法には特に
制約はない。即ち、（メタ）アクリル酸、クロトン酸、
マレイン酸、フマル酸、イタコン酸およびシトラコン酸
等の重合性不飽和カルボン酸或いはそれらの無水物等を
エチレン−酢酸ビニル共重合体の重合時に第三成分とし
て共重合させる方法或いはエチレン−酢酸ビニル共重合
体にグラフト重合または他の不飽和重合性単量体と共に
グラフト共重合させる方法や無水マレイン酸、フマル酸
またはイタコン酸等のジカルボン酸類をエチレン−酢酸
ビニル共重合体に付加させる方法等の常法を任意に選択
することによりカルボキシル基が導入される。また、例
えばエチレン−酢酸ビニル共重合体の部分加水分解物の
ヒドロキシル基をマレイン酸、フマル酸、イタコン酸等
の多価カルボン酸で半エステル化することによってカル
ボキシル基を導入する方法等の合成法を利用したもので
もよい。The ethylene-vinyl acetate copolymer (A) having a carboxyl group, which is a component of the resin mixture (D) for forming the heat-sealing film for packaging material of the present invention, is ethylene-
A vinyl acetate copolymer having a carboxyl group chemically bonded thereto is suitable, and there is no particular limitation on the method of introducing it. That is, (meth) acrylic acid, crotonic acid,
A method of copolymerizing a polymerizable unsaturated carboxylic acid such as maleic acid, fumaric acid, itaconic acid and citraconic acid or an anhydride thereof as a third component at the time of polymerization of an ethylene-vinyl acetate copolymer, or an ethylene-vinyl acetate copolymer. Conventional methods such as a method of graft-polymerizing a polymer or graft-copolymerizing with another unsaturated polymerizable monomer and a method of adding a dicarboxylic acid such as maleic anhydride, fumaric acid or itaconic acid to an ethylene-vinyl acetate copolymer are used. A carboxyl group is introduced by arbitrarily selecting the method. Further, for example, a synthetic method such as a method of introducing a carboxyl group by half-esterifying a hydroxyl group of a partial hydrolyzate of ethylene-vinyl acetate copolymer with a polyvalent carboxylic acid such as maleic acid, fumaric acid, and itaconic acid It may be one using.
また、エチレン−酢酸ビニル共重合体はエチレン、酢酸
ビニルおよびカルボキシル基含有単量体以外に他の変性
用単量体が共重合されていてもよい。In addition, the ethylene-vinyl acetate copolymer may be copolymerized with other modifying monomers in addition to ethylene, vinyl acetate and a carboxyl group-containing monomer.
これらのエチレン−酢酸ビニル共重合体はいずれも使用
が可能であるが、樹脂混合物（Ｄ）を製造するために組
み合わせるスチレン（共）重合体（Ｂ）に対する相溶性
の程度、融点、二次転移等の諸物性を考慮して適切なも
のを選択すればよい。Any of these ethylene-vinyl acetate copolymers can be used, but the degree of compatibility with the styrene (co) polymer (B) to be combined to produce the resin mixture (D), the melting point, the second transition Appropriate ones may be selected in consideration of various physical properties such as.
本発明の包装材用熱封緘性フィルムを成形するための樹
脂混合物（Ｄ）の第二の成分であるスチレン（共）重合
体（Ｂ）としてはスチレン単独重合体の他、ジェンモノ
マーとの共重合体、アクリロニトリルとの共重合体等広
く市販されているものを始めとして不飽和カルボン酸単
量体との共重合体や、種々の他の共単体との共重合体が
ありまたランダム共重合、グラフト共重合、ブロック共
重合などの重合様式の相違によっても種々の物性のもの
が得られるが、樹脂混合物（Ｄ）において配合される他
の成分、即ちカルボキシル基を有するエチレン−酢酸ビ
ニル共重合体（Ａ）および高密度ポリエチレン（Ｃ）の
有する諸物性を考慮して適宜選択する必要がある。The styrene (co) polymer (B), which is the second component of the resin mixture (D) for forming the heat-sealing film for a packaging material of the present invention, may be a styrene homopolymer or a copolymer with a gen monomer. Polymers, copolymers with acrylonitrile, etc., which are widely marketed, and copolymers with unsaturated carboxylic acid monomers, and copolymers with various other comonomers, and random copolymerization Although various physical properties can be obtained depending on the difference in the polymerization mode such as graft copolymerization, block copolymerization, etc., another component to be blended in the resin mixture (D), that is, ethylene-vinyl acetate copolymer having a carboxyl group. It is necessary to appropriately select it in consideration of various physical properties of the polymer (A) and the high-density polyethylene (C).
本発明の包装材用熱封緘性フィルムを成形するための樹
脂混合物（Ｄ）の第三の成分である高密度ポリエチレン
（Ｃ）は市販の製品がいずれも使用可能であるが、前記
の２成分との相溶性の程度によって適切なものを選択す
ればよい。As the high density polyethylene (C) which is the third component of the resin mixture (D) for molding the heat-sealing film for a packaging material of the present invention, any commercially available product can be used. An appropriate one may be selected depending on the degree of compatibility with.
本発明の包装材用熱封緘性フィルムの成形にあたっては
樹脂混合物（Ｄ）に対して、一般にプラスチックフィル
ムの製造時に使用される種々の配合剤類、例えば染料、
顔料、充填剤、滑剤、発泡剤、酸化防止剤、可塑剤等の
添加は必要に応じて任意に行ない得る。例えば、樹脂混
合物（Ｄ）に対して発泡剤を添加して成形すると熱封緘
性発泡フィルムが得られるがフィルムにクッション性が
付与されるため不均一な基材表面に対して密着性の向上
が期待されるなど通常のプラスチックフィルムにおいて
行なわれる手段は殆どそのまま適用され得る。In forming the heat-sealing film for a packaging material of the present invention, various compounding agents generally used in the production of a plastic film, such as a dye, are added to the resin mixture (D).
Addition of pigments, fillers, lubricants, foaming agents, antioxidants, plasticizers and the like can be performed as needed. For example, when a foaming agent is added to the resin mixture (D) and molded, a heat-sealing foamed film is obtained, but since the film is provided with cushioning properties, the adhesion to a non-uniform substrate surface is improved. The measures taken in ordinary plastic films, as expected, can be applied almost as is.
本発明の包装材用熱封緘性フィルムにおいて使用する熱
封緘性フィルムの成形法としては特に制限はなく、キャ
スティング法、インフレーション法、Ｔダイ押出し法、
カレンダー法等の通常のフィルム成形加工法がいずれも
適用可能であり、かつ延伸を加えることにより破裂性に
方向性を持たせ得るなどの処理方法も常法が殆ど適用で
きる。また、本発明の包装材用熱封緘性フィルムと同志
あるいは必要により他の熱封緘性フィルムと共押出しを
行なうことにより多層フィルムを成形することも可能で
ある。The method for molding the heat-sealing film used in the heat-sealing film for packaging material of the present invention is not particularly limited, and casting method, inflation method, T-die extrusion method,
Any ordinary film forming method such as a calendering method can be applied, and a usual method can also be applied as a processing method such that a rupture property can be given a direction by stretching. It is also possible to form a multilayer film by coextrusion with the heat-sealing film for packaging material of the present invention, or with other heat-sealing film if necessary.
また該熱封緘性フィルムの厚さについては特に制限は無
く積層すべき包装用基材の種類や厚さおよび強度等を考
慮して適宜、設定するべきものであるが、フィルム強度
や成形方法からの制約があり、通常は５乃至50μの範囲
のものが好ましい。The thickness of the heat-sealing film is not particularly limited and should be appropriately set in consideration of the type, thickness, strength, etc. of the packaging substrate to be laminated, but from the film strength and the molding method. However, the range of 5 to 50 μm is usually preferable.
本発明の包装材用熱封緘性フィルムを積層すべき包装用
基材としては前記したように制約はなく、アルミニゥム
箔等の金属基材、グラシン紙、模造紙、白ボール等の紙
類およびポリ塩化ビニル、ポリエチレン、ポリプロピレ
ン、ポリスチレン、ポリエチレンテレフタレート等の諸
種のプラスチックフィルムあるいはシート類など包装に
使用される基材類に対し適用できる。The heat-sealing film for a packaging material of the present invention is not limited as described above as a packaging base material on which a heat-sealing film is to be laminated, and a metal base material such as aluminum foil, glassine paper, imitation paper, paper such as white balls and poly It can be applied to various types of plastic films or sheets such as vinyl chloride, polyethylene, polypropylene, polystyrene, polyethylene terephthalate, and other substrates used for packaging.
本発明の包装材用熱封緘性フィルムと包装用基材との積
層工程についても特に制約はなく、装置としては平板プ
レス方式、ロールプレス方式等いずれの方式でもよく、
公知のラミネータがそのまま適用される。There is no particular restriction on the lamination step of the heat-sealing film for packaging material and the packaging base material of the present invention, and the apparatus may be any method such as a flat plate pressing method and a roll pressing method,
A known laminator is applied as it is.
積層方法としては包装用基材に本発明の包装材用熱封緘
性フィルムを直接、加熱圧着して融着させる方法も可能
であり、またラミネーション用の接着剤を使用して積層
することも可能であるが、ドライラミネーション法が最
も一般的である。ラミネーション用の接着剤は市販の有
機溶剤系或いは水性系、場合によってはホッメルト系の
製品を任意に使用出来る。As a lamination method, the heat-sealing film for packaging material of the present invention may be directly bonded to the packaging base material by heating and pressure bonding, and may be laminated by using an adhesive for lamination. However, the dry lamination method is the most common. As the lamination adhesive, a commercially available organic solvent-based or water-based adhesive, and in some cases, a homelt type product can be optionally used.
また特に本発明の易破裂包装材においては一般的に前記
熱封緘性フィルムの厚さおよびアルミニゥム箔の厚さが
それぞれ５乃至50μおよび５乃至30μの範囲にあり、且
つ複合材の厚さが15乃至60μの範囲にあることが更に易
破裂性およびカール防止効果にとって好ましい。In particular, in the easily rupturable packaging material of the present invention, the thickness of the heat-sealing film and the thickness of the aluminum foil are generally in the range of 5 to 50 μ and 5 to 30 μ, respectively, and the thickness of the composite material is 15 Further, it is more preferable for it to be in the range of 60 to 60 μm for easy bursting and curling prevention effect.
また該熱封緘性フィルムの厚さについては特に制限は無
く積層すべきアルミニゥム箔の厚さおよび強度や製品で
ある包装材の厚さ及び価格等を考慮して適宜、設定する
べきものであるが、フィルム強度や成形方法からの制約
があり、前記したように通常は５乃至50μの範囲のもの
が好ましい。The thickness of the heat-sealing film is not particularly limited and should be appropriately set in consideration of the thickness and strength of the aluminum foil to be laminated and the thickness and price of the packaging material as a product. However, there are restrictions from the film strength and the molding method, and as described above, the range of 5 to 50 μm is usually preferable.
本発明の易破裂性包装材において使用するアルミニゥム
箔としても制約はなく、硬質或いは軟質のいずれでも適
用可能である。厚さにも特に制限はないが前記したよう
に５乃至30μの厚さの物が好ましい。PTP包装用にアル
ミニゥム箔単独で通常、使用される10乃至30μの範囲の
ものをそのまま適用してもよい。しかし熱封緘性フィル
ムと積層されることにより材料全体の強度が向上するこ
とを考慮すれば５乃至25μのアルミニゥム箔が好まし
い。The aluminum foil used in the easily rupturable packaging material of the present invention is not limited, and either hard or soft can be applied. The thickness is not particularly limited, but as described above, a thickness of 5 to 30 μ is preferable. The aluminum foil alone used for PTP packaging, which is usually used in the range of 10 to 30 μ, may be applied as it is. However, considering that the strength of the whole material is improved by laminating it with the heat-sealing film, an aluminum foil having a thickness of 5 to 25 μ is preferable.
（作用及び効果） 本発明の包装材熱封緘性フィルムを成形するための樹脂
混合物（Ｄ）の成分であるカルボキシル基を有するエチ
レン−酢酸ビニル共重合体（Ａ）は自己熱封緘性および
アルミニゥム箔等の金属基材、グラシン紙、模造紙、白
ボール紙等の紙類およびポリ塩化ビニル、ポリエチレ
ン、ポリプロピレン、ポリスチレン、ポリエチレンテレ
フタレート等諸種のプラスチックフィルムあるいはシー
ト類などの包装材類に対する熱封緘性を与えるものであ
り、またフィルム強度等の機械的性質も主として、この
カルボキシル基を有するエチレン−酢酸ビニル共重合体
（Ａ）に依存するものである。(Operation and effect) The ethylene-vinyl acetate copolymer (A) having a carboxyl group, which is a component of the resin mixture (D) for forming the packaging material heat-sealing film of the present invention, is self-heat-sealing and aluminum foil. Heat-sealing property for metal base materials such as glass, paper such as glassine paper, imitation paper, white cardboard, and various plastic films or sheets such as polyvinyl chloride, polyethylene, polypropylene, polystyrene, polyethylene terephthalate, etc. In addition, the mechanical properties such as film strength mainly depend on the ethylene-vinyl acetate copolymer (A) having a carboxyl group.
本発明の包装材用熱封緘性フィルムの樹脂混合物（Ｄ）
の第二の成分であるスチレン（共）重合体（Ｂ）は樹脂
混合物（Ｄ）を成形して得られる熱封緘性フィルムに脆
性を与えて破裂抵抗値を小さくする効果を有する。Resin mixture of heat-sealing film for packaging material of the present invention (D)
The second component, styrene (co) polymer (B), has the effect of imparting brittleness to the heat-sealing film obtained by molding the resin mixture (D) and reducing the burst resistance value.
本発明の包装材用熱封緘性フィルムを成形するための樹
脂混合物（Ｄ）の第三の成分である高密度ポリエチレン
（Ｃ）は該包装材用熱封緘性フィルムの引裂き性に寄与
し、特に本発明の樹脂混合物（Ｄ）においては直線的に
任意の方向に引裂くことが出来るという性質が付与され
る。The high-density polyethylene (C) which is the third component of the resin mixture (D) for forming the heat-sealing film for packaging material of the present invention contributes to the tearability of the heat-sealing film for packaging material, The resin mixture (D) of the present invention has a property that it can be linearly torn in any direction.
本発明の包装用熱封緘性フィルムを成形するための樹脂
混合物（Ｄ）は少なくとも１種の、カルボキシル基を有
するエチレン・酢酸ビニル共重合体（Ａ）15〜50％、少
なくとも１種のスチレン（共）重合体（Ｂ）10〜60％お
よび少なくとも１種の高密度ポリエチレン（Ｃ）15〜40
％［ただし、（Ａ）＋（Ｂ）＋（Ｃ）＝100％である］
からなるが、カルボキシル基を有するエチレン−酢酸ビ
ニル共重合体（Ａ）の混合物割合が15％以下になると樹
脂混合物（Ｄ）を成形して得られる熱封緘性フィルムの
熱封緘性が低下し、反対に50％以上になると熱封緘性は
向上して接着強度は大きくなるが熱封緘性フィルムの強
度が大きくなるとともに伸びも大きくなるために引裂き
や破裂に対する抵抗力が大きくなるため不適当である。The resin mixture (D) for forming the heat-sealing film for packaging of the present invention comprises at least one ethylene-vinyl acetate copolymer having a carboxyl group (A) 15 to 50% and at least one styrene ( Co) polymer (B) 10-60% and at least one high-density polyethylene (C) 15-40
% [However, (A) + (B) + (C) = 100%]
However, when the mixture ratio of the ethylene-vinyl acetate copolymer (A) having a carboxyl group is 15% or less, the heat-sealing property of the heat-sealing film obtained by molding the resin mixture (D) decreases, On the other hand, if it is 50% or more, the heat-sealing property is improved and the adhesive strength is increased, but the strength of the heat-sealing film is increased and the elongation is also increased, which is unsuitable because the resistance against tearing and rupture is increased. .
またスチレン（共）重合体（Ｂ）の混合物割合が10％以
下であると樹脂混合物（Ｄ）を成形して得られる熱封緘
性フィルムの脆性が減少し、伸びが大きくなるため引裂
きや破裂を起こし難くなり、起こっても不完全なため、
包装体にした場合には内容物の取り出しが円滑に行なわ
れない。60％を越える場合には脆性が大きくなり過ぎる
ためにフィルムの成形ができなくなり、成形できた場合
においても取り扱い作業が困難である。When the mixture ratio of the styrene (co) polymer (B) is 10% or less, the brittleness of the heat-sealing film obtained by molding the resin mixture (D) is reduced and the elongation is increased, so that tearing or rupture occurs. It ’s hard to wake up, and even if it happens, it ’s incomplete,
In the case of a package, the contents cannot be taken out smoothly. If it exceeds 60%, the brittleness becomes too large and the film cannot be formed. Even if the film can be formed, the handling work is difficult.
高密度ポリエチレン（Ｃ）の混合割合は15％以下の場合
には樹脂混合物（Ｄ）を成形して得られる熱封緘性フィ
ルムの引裂き性が低下し、任意の方向に引裂けなくな
り、また破裂させた場合に一方向のみに裂けて簾状にな
って内容物が取出せないという現象をしばしば生ずる。
40％以上の場合には熱封緘性が低下して所要の接着強度
が得られない。When the mixing ratio of the high-density polyethylene (C) is 15% or less, the tearability of the heat-sealing film obtained by molding the resin mixture (D) is deteriorated, and the heat-sealing film does not tear in any direction or is ruptured. When it does, it often tears in only one direction, forming a blind shape, and the phenomenon that the contents cannot be taken out often occurs.
When it is 40% or more, the heat sealing property is deteriorated and the required adhesive strength cannot be obtained.
尚、前記の諸特性の他に本発明の包装用熱封緘性フィル
ムには高温の雰囲気中に暴露されても収縮を起こす傾向
が小さい特徴があり、包装体を変形させたり、接着面の
剥離を生じたりすることによる損失が少なくなる。In addition to the various characteristics described above, the heat-sealing film for packaging of the present invention has a characteristic that it has a small tendency to cause shrinkage even when exposed to a high temperature atmosphere, and thus deforms the package or peels the adhesive surface. The loss due to the occurrence of is reduced.
また前記熱封緘性フィルムは樹脂混合物（Ｄ）の組成に
よって半透明乃至不透明のものが得られるので、包装用
基材に積層することにより反射光線を散乱させるので艷
消面とする効果があり、しかも熱封緘を行なった部分も
不透明性の程度が変化することがないので例えばアルミ
ニゥム箔の艷面に積層することにより艷消面と同様の外
観にすることが出来る。Further, since the heat-sealing film can be translucent or opaque depending on the composition of the resin mixture (D), it has an effect of being a masking surface because it scatters reflected light by laminating it on a packaging base material. Moreover, since the degree of opacity does not change in the heat-sealed portion, the appearance can be made similar to that of the vanishing surface by, for example, laminating it on the aluminum foil.
以下、実施例によって更に詳細に説明する。Hereinafter, further details will be described with reference to examples.
［実施例１］ モディックＥ−300H（三菱油化（株）製カルボキシル基
変性エチレン−酢酸ビニル共重合体；メチルトインデッ
クス2.5、比重0.95、ビカット軟化点43℃）33部とダイ
ヤレックスHT−516（三菱モンサント化成工業（株）製
ポリスチレン樹脂；メルトインデックス2.2、比重1.0
5、ビカット軟化点94℃）50部およびハイゼックス5305E
（三井石油化学工業（株）製高密度ポリエチレン；メル
トインデックス0.8、比重0.95、ビカット軟化点122℃）
17部とを混合して樹脂混合物を作成し、インフレーショ
ンフィルム押出し成形機を使用してシリンダー温度160
℃、ダイス温度197℃の条件下で厚さ30μの熱封緘性フ
ィルムを製造した。[Example 1] 33 parts of Modic E-300H (carboxyl group-modified ethylene-vinyl acetate copolymer manufactured by Mitsubishi Petrochemical Co., Ltd .; methylt index 2.5, specific gravity 0.95, Vicat softening point 43 ° C) and Dialex HT-516 (Polystyrene resin manufactured by Mitsubishi Monsanto Kasei Co., Ltd .; melt index 2.2, specific gravity 1.0
5, Vicat softening point 94 ℃) 50 parts and Hi-Zex 5305E
(Mitsui Petrochemical Industry Co., Ltd. high density polyethylene; melt index 0.8, specific gravity 0.95, Vicat softening point 122 ° C)
A resin mixture was prepared by mixing with 17 parts, and a cylinder temperature of 160 was obtained using an inflation film extrusion molding machine.
A heat-sealing film having a thickness of 30 μm was produced under the conditions of ℃ and die temperature of 197 ℃.
得られたフィルムに直径約3mmのポリエチレン製のスト
ローの先端を押しつけて、やや圧力を加えると容易にス
トローの先端にそって円形の孔が開いて貫通した。When the tip of a polyethylene straw having a diameter of about 3 mm was pressed against the obtained film and a slight pressure was applied, a circular hole was easily opened along the straw tip and penetrated.
このフィルムを厚さ20μの軟化アルミニゥム箔にポリウ
レタン系の二液性ドライラミネーション用接着剤（武田
薬品工業（株）製、タケラックA310/タケネートＡ−
３）を使用して貼り合せて、厚さ約50μの包装用基材を
作成した。This film is applied to a soft aluminum foil with a thickness of 20μ and a polyurethane adhesive for two-component dry lamination (Takelac A310 / Takenate A- manufactured by Takeda Pharmaceutical Co., Ltd.).
3) was used for bonding to prepare a packaging base material having a thickness of about 50 μm.
この包装用基材を熱封緘性フィルム面同志を対抗面とし
て合せて熱封緘温度130℃、圧力3kg./cm2.、加圧時間１
秒前の条件で熱封緘し、熱封緘部を手で引裂いたが任意
の方向に容易に直線的に裂け、切口は鋸歯状になったり
毛羽立ったりせず奇麗であった。This packaging base material is combined with the heat-sealing film surfaces facing each other and the heat-sealing temperature is 130 ° C, pressure is 3 kg./cm 2 , pressure time is 1
It was heat-sealed under the condition of a few seconds before, and the heat-sealed part was torn by hand, but it was easily torn linearly in any direction, and the cut was neat without sawing or fluffing.
また前記の包装用基材を厚さ250μのポリプロピレン・
シートに熱封緘温度180℃、圧力3kg./cm2.、加圧時間１
秒間の条件下で熱封緘して熱封緘性試験用の試料を作成
した。この試料について180度剥離試験（15mm幅）を行
なったところ1.38kgであった。用途により必要とされる
熱封緘接着強度は異るが、通常、PTP包装、ストリップ
包装等においては1kg以上であれば満足すべきものとさ
れる。In addition, the packaging base material is 250 μm thick polypropylene
Sheet heat sealing temperature 180 ℃, pressure 3kg./cm 2 , pressure time 1
Heat sealing was performed under the condition of 2 seconds to prepare a sample for the heat sealing property test. When the 180-degree peeling test (15 mm width) was performed on this sample, it was 1.38 kg. Although the heat-sealing adhesive strength required depends on the application, it is usually satisfactory for PTP packaging, strip packaging, etc. if it is 1 kg or more.
同様にして、この包装用基材を厚さ250μの硬質塩化ビ
ニル樹脂シートに熱封緘温度130℃、圧力5kg/cm2、加圧
時間１秒前の条件下で熱封緘を行ない、熱封緘性試験用
試料を作成し、180℃剥離強度を測定したところ、1.24k
gであった。Similarly, this packaging substrate was heat-sealed on a hard vinyl chloride resin sheet having a thickness of 250μ under conditions of heat-sealing temperature of 130 ° C, pressure of 5 kg / cm 2 and pressurizing time of 1 second. When a test sample was prepared and the 180 ° C peel strength was measured, it was 1.24k.
It was g.
また、前記の二種のプラスチック基材シートに熱封緘を
行なった試料について、カールの大きさを20mmの長さの
試料片がカールによって円弧を描くときの弦の長さ、即
ちその時の両縁間の距離によって測定した。実用上、16
mm以下にならないことが好ましいが、基材がポリロピレ
ン・シートおよび塩化ビニル樹脂シートの各場面につい
て、それぞれ18.0mmおよび18.7mmの値が得られた。Regarding the samples obtained by heat-sealing the above two types of plastic substrate sheets, the curl size is the length of the chord when the sample piece with a length of 20 mm draws an arc by curling, that is, both edges at that time. It was measured by the distance between them. 16 in practical use
Although it is preferable that the thickness is not less than mm, values of 18.0 mm and 18.7 mm were obtained for each of the scenes where the substrate was a polypropylene sheet and a vinyl chloride resin sheet, respectively.
次に包装材の破裂強さ（JIS P8112）及び巾15mm当りの
引張り強さを測定した。破裂強さは2kg/cm2を超えるとP
TP包装等が押圧により破り難くなり、取り扱い上の必要
強度としては引張り強さとして2kg以上あればよいとさ
れる。本実施例の包装材の破裂強さは1.3kg./cm2、引張
り強さは2.6kgの値が得られた。Next, the burst strength (JIS P8112) of the packaging material and the tensile strength per 15 mm width were measured. Burst strength is P when exceeding 2 kg / cm 2.
It is difficult for the TP package to break due to pressure, and it is said that the required tensile strength for handling is 2 kg or more. The packaging material of this example had a burst strength of 1.3 kg./cm 2 and a tensile strength of 2.6 kg.
更に前記の厚さ250μのポリプロピレン・シートおよび
塩化ビニル樹脂シートに医薬用カプセル格納用のポケッ
トを成形し、前記の熱封緘強度試験の場合と同一条件
で、本実施例の包装用基材を蓋材として使用し、カプセ
ルを格納して熱封緘してそれぞれPTP包装体を作成し
た。いずれも包装体としては十分な強度があり、かつ指
頭で容器底部を押圧すると簡単に蓋材が破裂してカプセ
ルを容易に取り出すことが出来た。Further, a 250 μm thick polypropylene sheet and a vinyl chloride resin sheet were molded into pockets for storing pharmaceutical capsules, and the packaging base material of this example was covered under the same conditions as in the heat-sealing strength test. Used as materials, the capsules were stored and heat-sealed to make PTP packages. Each of them had sufficient strength as a package, and when the bottom of the container was pressed with a fingertip, the lid material easily ruptured and the capsule could be easily taken out.
［実施例２］ 実施例１において、モディックＥ−300Hを26部、ダイヤ
レックスHT−516を40部およびハイゼックス5305Eを34部
とを混合して樹脂混合物を作成し、インフレーションフ
ィルム押し出し成形機を使用して同様に成形して20μの
熱封緘性フイルムを製造した。[Example 2] In Example 1, 26 parts of Modic E-300H, 40 parts of Dialex HT-516 and 34 parts of HiZex 5305E were mixed to prepare a resin mixture, and an inflation film extrusion molding machine was used. Then, the film was molded in the same manner to manufacture a 20 μ heat-sealing film.
得られた熱封緘性フィルムに直径約3mmのポリエチレン
製のストローの先端を突き刺したところ、実施例１の場
合と同様に容易に貫通した。When the end of a polyethylene straw having a diameter of about 3 mm was pierced into the obtained heat-sealing film, it easily penetrated as in the case of Example 1.
前記熱封緘性フィルムを厚さ15μの軟質アルミニゥム箔
と貼り合せて厚さ約35μの包装用基材を作成した。The heat-sealing film was bonded to a soft aluminum foil having a thickness of 15 μm to prepare a packaging base material having a thickness of about 35 μm.
この包装用基材について実施例１の場合と同様に諸特性
を測定した。Various properties of this packaging substrate were measured in the same manner as in Example 1.
即ち、前記包装用基材同志を熱封緘した試料の引裂き性
は実施例１の場合と同様に良好であった。That is, the tearability of the sample obtained by heat-sealing the packaging base materials was good as in the case of Example 1.
また、熱封緘強度はポリプロピレン・シートに対して1.
28kg、塩化ビニル樹脂シートに対して1.15kgであり、カ
ール度はポリプロピレン・シートおよび塩化ビニル樹脂
シートの各場合について、それぞれ17.5mmおよび18.0mm
であった。Also, the heat sealing strength is 1.
28 kg, 1.15 kg for vinyl chloride resin sheet, and the degree of curl is 17.5 mm and 18.0 mm for polypropylene sheet and vinyl chloride resin sheet, respectively.
Met.
破裂強さおよび引張り強さは、それぞれ1.8kg/cm2およ
び4.3kgであった。The burst strength and tensile strength were 1.8 kg / cm 2 and 4.3 kg, respectively.
次に本実施例の熱封緘性フィルムを厚さ35μのグラシン
紙に直接、180℃の圧着ロールを通すことにより積層し
て包装用基材を作成したが引裂き性は良好であり、熱封
緘強度はポリプロピレン・シートおよび塩化ビニル樹脂
シートに対してそれぞれ1.04kg.および1.03kg.カール度
はそれぞれ18.3mmおよび18.8mm、引張り強さおよび破裂
強さは、それぞれ2.7kg.および1.46kg./cm2.であった。Next, the heat-sealing film of this example was laminated directly on glassine paper having a thickness of 35 μ by passing it through a pressure roll of 180 ° C. to form a packaging base material, which has good tearability and heat-sealing strength. Is 1.04 kg. And 1.03 kg for polypropylene sheet and vinyl chloride resin sheet respectively. Curling degree is 18.3 mm and 18.8 mm respectively, and tensile strength and burst strength are 2.7 kg. And 1.46 kg./cm 2 , respectively. .Met.
［比較例１］ 実施例１で使用した厚さ20μの軟質アルミニゥム箔にポ
リプロピレン・シート用熱封緘剤としてハードレン13−
Ｌ（東洋化成工業（株）製、塩素化ポリプロピレン溶
液、塩素含量26％不揮発分30％トルエン溶液）を、塩化
ビニル樹脂シート用としてディックシール−100Z−３
（大日本インキ化学（株）製塩化ビニル−酢酸ビニル共
重合体系溶液、不揮発分25％メチルエチルケトン／トル
エン溶液）をそれぞれ5g./m2（固形分）の割合で塗工、
乾燥して通常のPTP蓋材として使用される塗布型の包装
用基材を作成し、実施例１の場合と同様に諸特性を測定
した。Comparative Example 1 A soft aluminum foil having a thickness of 20 μm used in Example 1 was hardened as a heat sealing agent for polypropylene sheets 13-
L (Toyo Kasei Co., Ltd., chlorinated polypropylene solution, chlorine content 26%, non-volatile content 30% toluene solution) was used as a vinyl chloride resin sheet for Dickseal-100Z-3.
(Dainippon Ink and Chemicals Co., Ltd. vinyl chloride-vinyl acetate copolymer solution, non-volatile content 25% methyl ethyl ketone / toluene solution) was applied at a rate of 5 g./m 2 (solid content), respectively.
After drying, a coating type packaging base material used as an ordinary PTP lid material was prepared, and various properties were measured in the same manner as in Example 1.
引裂き性は良好であるが、熱封緘強度はポリプロピレン
・シートに対しては0.91kgと低く、塩化ビニル樹脂シー
トに対しては1.6kgであった。カール度はポリプロピレ
ン・シートおよび塩化ビニル樹脂シートの各場合につい
て、それぞれ14.8mmおよび15.3mmでいずれも大きく作業
工程上に問題がある。Tearability was good, but heat sealing strength was low at 0.91 kg for polypropylene sheets and 1.6 kg for vinyl chloride resin sheets. The degree of curl is 14.8 mm and 15.3 mm for each of the polypropylene sheet and the vinyl chloride resin sheet, respectively, and both have a problem in the working process.
破裂強さはポリプロピレン・シート用の包装用基材につ
いては1.8kg/cm2であったが、塩化ビニル樹脂シート用
の包装用基材に対しては3.3kg/cm2と大きかったが、引
張り強さでは、それぞれ2kgおよび2.1kgであった。The burst strength was 1.8 kg / cm 2 for the polypropylene base sheet packaging material and 3.3 kg / cm 2 for the vinyl chloride resin sheet packaging base material. The strength was 2 kg and 2.1 kg, respectively.
上記の二種の包装用基材を基材シートを交換して熱封緘
を行なったが、いずれも全く接着性を示さなかった。The above-mentioned two types of packaging substrates were heat-sealed by exchanging the substrate sheets, but neither showed adhesiveness at all.
［比較例２］ モディックＥ−300H、ダイヤレックスHT−516およびハ
イゼックス5305Fの配合量を12部、50部および38部とし
て樹脂混合物を作成し、実施例１と同様にして厚さ30μ
の熱封緘性フィルムを製造し、厚さ20μの軟質アルミニ
ゥム箔に貼り合せて、厚さ約50μの包装用基材を作成し
たが、この包装用基材はポリプロピレン・シートおよび
塩化ビニル樹脂シートのいずれに対しても接着強度が0.
3kg.以下で殆ど接着性を示さなかった。[Comparative Example 2] A resin mixture was prepared with the compounding amounts of Modic E-300H, Dialex HT-516 and HiZex 5305F being 12, 50 and 38 parts, and the thickness was 30 μm in the same manner as in Example 1.
The heat-sealing film was manufactured and laminated on a soft aluminum foil with a thickness of 20μ to make a packaging base material with a thickness of about 50μ.The packaging base material is polypropylene sheet or vinyl chloride resin sheet. Adhesive strength is 0 for both.
Almost no adhesion was exhibited at 3 kg. Or less.
［比較例３］ 実施例１においてモディックＥ−300H、ダイヤレックス
HT−516およびハイゼックス5305Eの配合量をそれぞれ60
部、23部および17部とした以外は全く同様に処理を行な
って厚さ30μの熱封緘性フィルムを製造し、さらに厚さ
約50μの包装用基材を作成した。[Comparative Example 3] Modid E-300H, Dialex in Example 1
The amount of HT-516 and Hi-Zex 5305E is 60 each.
The heat-sealing film having a thickness of 30 μm was manufactured by the same treatment except that the amount of the heat-sealing film was 30 parts, 23 parts and 17 parts, and a packaging base material having a thickness of about 50 μm was prepared.
得られた熱封緘性フィルムに直径約3mmのポリエチレン
製のストローの先端を押しつけて、圧力を加えたが容易
に貫通せず殆どストローが折れ曲がることが多かった。The end of a polyethylene straw having a diameter of about 3 mm was pressed against the obtained heat-sealing film, and pressure was applied, but the straw did not penetrate easily and the straw was often bent.
包装用基材については引裂き製が不良で、抵抗が大きく
切り口が毛羽立つ傾向があり、破裂強さが2.7kg/cm2と
大きかったので、実施例１と同様にしてポリプロピレ
ン．シートおよび塩化ビニル樹脂シートに医薬品カプセ
ル格納用のポケットを成形したものに、本比較例の包装
用基材を蓋材として使用し、カプセルを格納して熱風緘
を行ない、それぞれPTP包装体を作成したところ、いず
れも包装体として十分な強度はあるが容器底部を指頭で
押圧しても簡単に蓋材が破裂せず、大きな圧力を加える
と容器が変形するかカプセルは容易に取り出すことが出
来なかった。As for the packaging base material, the tearability was poor, the resistance was large, the cut end tended to be fluffed, and the burst strength was as large as 2.7 kg / cm 2. Therefore, polypropylene was used in the same manner as in Example 1. A sheet and a vinyl chloride resin sheet molded with pockets for storing drug capsules, using the packaging base material of this comparative example as a lid material, storing the capsules and performing hot air sieving to create PTP packages. All of them have sufficient strength as a package, but even if the bottom of the container is pressed with a fingertip, the lid does not burst easily, and if a large pressure is applied, the container will be deformed or the capsule can be easily taken out. There wasn't.
［比較例４］ 実施例１においてモディックＥ−300H、ダイヤレックス
HT−516およびハイゼックス5305Eの配合量をそれぞれ60
部、23部および17部とした以外は全く同様に処理を行な
って厚さ30μの熱封緘性フィルムを製造し、さらに厚さ
約50μの包装用基材を作成してた。[Comparative Example 4] In Example 1, Modic E-300H, Dialex
The amount of HT-516 and Hi-Zex 5305E is 60 each.
The heat-sealing film having a thickness of 30 μm was produced by the same treatment except that the parts were made to be 23 parts, 23 parts and 17 parts, and a packaging base material having a thickness of about 50 μm was prepared.
得られた熱封緘性フィルムは強靱であるとともに伸びが
大きく、ストローの先端で圧迫してもフィルムが伸びる
ために貫通し難いという現象が生じた。引裂き性も不良
でアルミニゥム箔が裂けても熱封緘性フィルム層が容易
に破れなかった。また、破裂性の測定では熱封緘性フィ
ルム層が伸びるために一定の値が得られず、実施例１と
同様にしてポリプロピレン・シートおよび塩化ビニル樹
脂シートに医薬用カプセル格納用のポケットを成形した
ものに、本比較例の包装用基材を蓋材として使用し、カ
プセルを格納して熱封緘を行ない、それぞれPTP包装体
を作成したところ、いずれも包装体として十分な強度は
あるが容器底部を指頭で押圧してもアルミニゥム箔が破
れても熱封緘性フィルムで繋っているためにカプセルは
取り出すことが出来なかった。The obtained heat-sealing film was tough and had a large elongation, and there was a phenomenon that it was difficult to penetrate because the film expanded even when pressed by the tip of the straw. The tearability was also poor, and the heat-sealing film layer was not easily torn even when the aluminum foil was torn. Further, in the measurement of rupture property, a constant value could not be obtained because the heat-sealing film layer stretched, and a polypropylene sheet and a vinyl chloride resin sheet were formed with pockets for storing pharmaceutical capsules in the same manner as in Example 1. Using the packaging base material of this comparative example as a lid material, the capsules were stored and heat-sealed, and PTP packages were created. Even if the finger was pressed with the fingertip, the capsule could not be taken out because the aluminum foil was torn and the heat-sealing film was used for connection.
［比較例５］ 実施例１においてモディックＥ−300H、ダイヤレックス
HT−516およびハイゼックス5305Eの配合量をそれぞれ15
部、70部および15部とした以外は全く同様に処理を行な
って厚さ30μの熱封緘性フィルムを製造しようとしたと
ころ非常に脆いためにフィルムの破断が頻繁に起こり製
造できなかった。[Comparative Example 5] In Example 1, Modic E-300H, Dialex
The amount of HT-516 and Hi-Zex 5305E is 15 each.
When a heat-sealing film having a thickness of 30 μm was tried to be produced by the same treatment except that the amount was 70 parts, 70 parts and 15 parts, the film was very fragile and could not be manufactured.
［比較例６］ 実施例１においてモディックＥ−300H、ダイヤレックス
HT−516およびハイゼックス5305Eの配合量をそれぞれ33
部、57部および10部とした以外は全く同様に処理を行な
って厚さ30μの熱封緘性フィルムを製造し、さらに厚さ
約50μの包装用基材を作成した。[Comparative Example 6] In Example 1, Modic E-300H, Dialex
The amount of HT-516 and Hi-Zex 5305E is 33 each.
The heat treatment film having a thickness of 30 μm was produced by the same treatment as described above except that the amount was 57 parts, 57 parts and 10 parts, and a packaging base material having a thickness of about 50 μm was prepared.
この包装用基材は引裂き方向によっては抵抗の大きい場
合があり、毛羽立つことがある。This packaging base material may have a high resistance depending on the tearing direction, and may fluff.
また、破裂強さは1.2kg/cm2で良好であったが、実施例
１と同様にしてポリプロピレン・シートおよび塩化ビニ
ル樹脂シートに医薬品カプセル格納用のポケットを成形
したものに、本比較例の包装用基材を蓋材として使用
し、カプセルを格納して熱封緘を行なって、それぞれPT
P包装体を作成し容器底部を指頭で押圧したところ容易
に蓋材が破裂したが数本の裂け目が一定方向に生成して
簾状となっているためカプセルは簡単に押し出すことが
できなかった。Although the burst strength was 1.2 kg / cm 2 , which was good, the polypropylene sheet and the vinyl chloride resin sheet were molded with pockets for storing drug capsules in the same manner as in Example 1, and Using the packaging base material as the lid material, the capsules are stored and heat sealed, and
When the P package was created and the bottom of the container was pressed with the fingertips, the lid material ruptured easily, but several crevices were generated in a certain direction and became a blind, so the capsule could not be easily pushed out. .
［比較例７］ 実施例１においてモディックＥ−300H、ダイヤレックス
HT−516およびハイゼックス5305Eの配合量をそれぞれ33
部、17部および50部とした以外は全く同様に処理を行な
って厚さ30μの熱封緘性フィルムを製造し、さらに厚さ
約50μの包装用基材を作成した。[Comparative Example 7] Modid E-300H, Dialex in Example 1
The amount of HT-516 and Hi-Zex 5305E is 33 each.
The same treatment was carried out except that the parts, 17 parts, and 50 parts were used to produce a heat-sealing film having a thickness of 30 μm, and a packaging base material having a thickness of about 50 μm was prepared.
この包装用基材の熱封緘強度はポリプロピレン・シート
および塩化ビニル樹脂シートに対してそれぞれ0.41kg.
および0.38kg.であり殆ど所要の接着性を示さなかっ
た。The heat sealing strength of this packaging base material is 0.41 kg for polypropylene sheet and vinyl chloride resin sheet, respectively.
And 0.38 kg., Which showed almost no required adhesiveness.
Claims (1)
るエチレン・酢酸ビニル共重合体（Ａ）15〜50％（重量
％、以下すべて同様である）、少なくとも１種のスチレ
ン（共）重合体（Ｂ）10〜60％および少なくとも１種の
高密度ポリエチレン（Ｃ）15〜40％［ただし、（Ａ）＋
（Ｂ）＋（Ｃ）＝100％である］からなる重合体混合物
（Ｄ）を成形してなることを特徴とする包装材用熱封緘
性フィルム。1. At least one kind of ethylene / vinyl acetate copolymer (A) having a carboxyl group (A) 15 to 50% (% by weight, the same applies hereinafter) and at least one kind of styrene (co) polymer ( B) 10-60% and at least one high density polyethylene (C) 15-40% [(A) +
(B) + (C) = 100%] is formed by molding a polymer mixture (D), which is a heat-sealing film for packaging material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5339588A JPH0768363B2 (en) | 1988-03-07 | 1988-03-07 | Heat-sealing film for packaging materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5339588A JPH0768363B2 (en) | 1988-03-07 | 1988-03-07 | Heat-sealing film for packaging materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01225639A JPH01225639A (en) | 1989-09-08 |
| JPH0768363B2 true JPH0768363B2 (en) | 1995-07-26 |
Family
ID=12941635
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5339588A Expired - Lifetime JPH0768363B2 (en) | 1988-03-07 | 1988-03-07 | Heat-sealing film for packaging materials |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0768363B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5046380B2 (en) * | 2007-04-17 | 2012-10-10 | 株式会社エムエーパッケージング | Container lid with excellent straw piercing properties |
-
1988
- 1988-03-07 JP JP5339588A patent/JPH0768363B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01225639A (en) | 1989-09-08 |
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