JPH0460020B2 - - Google Patents
Info
- Publication number
- JPH0460020B2 JPH0460020B2 JP59167338A JP16733884A JPH0460020B2 JP H0460020 B2 JPH0460020 B2 JP H0460020B2 JP 59167338 A JP59167338 A JP 59167338A JP 16733884 A JP16733884 A JP 16733884A JP H0460020 B2 JPH0460020 B2 JP H0460020B2
- Authority
- JP
- Japan
- Prior art keywords
- heat
- eaa
- sealing
- film
- melt
- 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
- 229920001577 copolymer Polymers 0.000 claims description 17
- 239000010410 layer Substances 0.000 claims description 16
- 239000002131 composite material Substances 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 239000012793 heat-sealing layer Substances 0.000 claims description 6
- 238000004898 kneading Methods 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims description 3
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 claims description 3
- 239000004711 α-olefin Substances 0.000 claims description 3
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 14
- 238000007789 sealing Methods 0.000 description 12
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 5
- 239000004677 Nylon Substances 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920006284 nylon film Polymers 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
Description
（産業上の利用分野）
本発明は良好なヒートシール特性を有するヒー
トシール性良好な複合フイルムに関する。
（従来の技術）
各種樹脂から積層構成された、いわゆる複合フ
イルムが包装材料分野に多量使用されている。こ
れらのフイルムは、一般に比較的低い融点の樹脂
からなるヒートシール層を有している。このよう
なヒートシール層の樹脂には次のような特性が要
求される。(1)他樹脂に対する接着性が良好なこ
と、(2)低温度でのヒートシールが可能でヒートシ
ールの適正温度範囲が広いこと、(3)ヒートシール
直後の剥離抵抗力、いわゆるホツトタツクが大き
いこと、(4)引張強度等の機械的強度が大きいこと
等が挙げられる。本発明者らは、比較的低融点の
エチレン−アクリル酸共重合体（以下「EAA」
という。）単体をヒートシール層に使用すべく
種々検討した。
（発明が解決しようとする問題点）
しかしながら、EAAの結晶構造等に起因する
透明性の低下や結晶融点を越える温度域での急激
な低粘度溶融体への変化等により、上述したヒー
トシール層に要求される特性（ヒートシール特
性）を満足するものは得られなかつた。
（問題点を解決するための手段）
本発明は上記の特性を満足できるヒートシール
層を見出したものであり、その要旨とするところ
は、
エチレンが50重量％以上で、かつアクリル酸を
３〜15重量％含むエチレン−アクリル酸共重合体
と、α−オレフイン及びα，β−不飽和カルボン
酸よりなる共重合体中に一種類以上の金属イオン
を分散含有しているイオン性共重合体とを溶融混
練してなる層をヒートシール層としたことを特徴
とするヒートシール性良好な複合フイルムにあ
る。
以下本発明を詳しく説明する。なお以下の説明
で、比率を示す「％」は「重量％」をあらわす。
本発明におけるEAAとは、エチレンとアクリ
ル酸を必須成分とする共重合体であつて、他のオ
レフインやアクリル酸以外の不飽和カルボン酸類
が共重合されていてもよい。エチレンモノマー単
位の共重合比率は50％以上で、かつアクリル酸の
モノマー単位の共重合比率は３〜15％の範囲とす
る。アクリル酸が３％未満の場合はヒートシール
特性の改良がみられず、15％を越える場合は溶融
粘度が低くすぎて成形性が悪くなる。
また、α−オレフイン及びα，β−不飽和カル
ボン酸よりなる共重合体中に一種類以上の金属イ
オンを分散含有しているイオン性共重合体（以下
「イオン性共重合体」という）は、通常のアイオ
ノマーが使用出来、例えばエチレン−メタアクリ
ル酸共重合体のNaイオンとの部分塩（Naタイ
プ）やZnイオンとの部分塩（Znタイプ）等が挙
げられる。
本発明では、上記EAAとイオン性共重合体と
を、溶融混練する必要があり両樹脂の混合比率は
EAA95〜〜50％に対し、イオン性共重合体５〜
50％の範囲が好ましい。イオン性共重合体が５％
未満のものは、ヒートシール性の改良効果が見ら
れず、50％を越すものは、増加の割には改良効果
が見られず不経済である。
溶融混練の方法は各種製造方法による製膜時に
行なえるが、ヒートシール層として用いる場合に
は、他樹脂との共押出し法が好適に適用できる。
本発明では、製膜時の溶融混練により、顕著な
メルトインデツクスの変化がみられ、例えばメル
トインデツクス2.0のEAAとメルトインデツクス
2.5のイオン性共重合体を同一量使用し、溶融混
練したところ、樹脂のメルトインデツクスが1.5
となつた。また、同様に溶融粘度特性にも第１図
に示すように顕著な変化がみられる。第１図は溶
融樹脂の見掛け粘度と温度との関係曲線を示すグ
ラフであつて、高化式フローテスターにより荷重
40Kg／cm2、ノズル１×２mmφで測定したものであ
る。
第１図の曲線Ａはメルトインデツクス7.0の
EAAを示し、このEAAにイオン性共重合体（メ
ルトインデツクス1.0）を一定比率で混合し、溶
融混練した樹脂は、曲線Ｂ（EAA／イオン性共重
合体＝80／20）及び曲線Ｃ（EAA／イオン性共重
合体＝60／40）に示すように、顕著に高粘度側ヘ
シフトしていることが判る。
このようなメルトインデツクスや溶融粘度の変
化の理由は明確ではないが、イオン性共重合体に
含有されている金属イオンがEAAの酸基と加熱
溶融混練によつて、化学的な相互作用を起こすた
めと考えられる。
つぎに本発明を実施例により、詳細に説明す
る。
（実施例）
実施例 １〜４
表−１に示す樹脂組成のEAA及びイオン性共
重合体を表−１に示す比率でミキサーにより混合
した後、口径30mm、Ｌ／Ｄ＝25の単軸押出機によ
り、Ｔダイを使用して厚さ100μのフイルムを採
取した。
得られた各フイルムについて、各種物性を測定
し、その結果を表−１に示した。
比較例 １〜３
比較例１，２については、上記実施例において
使用したEAAを単独で使用し、また、比較例３
は通常の低密度ポリエチレン（LDPE）を使用し
て、実施例と同一の製膜を行ない、得られたフイ
ルムの物性を測定した。
物性測定方法：
「MI」はメルトインデツクスをJISK−7210に
準拠して測定。同様に「ヘーズ」はJISK−7105、
及び「引張強度」はJISK−6761に準拠して測定
した。
「ナイロン接着性」については、各フイルムを
厚さ60μのナイロンフイルム（６−ナイロン製）
に載置し、100℃の加熱ロール間で仮接着後、オ
ープン中（200℃、１分間）で加熱接着し、引張
速度200mm／分でのＴ型剥離強度を測定したもの
である。
(Industrial Application Field) The present invention relates to a composite film with good heat-sealing properties. (Prior Art) A large amount of so-called composite films, which are laminated from various resins, are used in the field of packaging materials. These films generally have a heat seal layer made of a relatively low melting point resin. The resin for such a heat seal layer is required to have the following properties. (1) Good adhesion to other resins, (2) Heat sealing is possible at low temperatures and has a wide appropriate temperature range, (3) High peel resistance immediately after heat sealing, so-called hot tack. and (4) high mechanical strength such as tensile strength. The present inventors have developed an ethylene-acrylic acid copolymer (hereinafter referred to as "EAA") with a relatively low melting point.
That's what it means. ) Various studies were conducted to use the single substance as a heat seal layer. (Problems to be Solved by the Invention) However, the above-mentioned heat seal layer However, it was not possible to obtain a product that satisfied the properties required for (heat sealing properties). (Means for Solving the Problems) The present invention has discovered a heat-sealing layer that satisfies the above characteristics, and its gist is that ethylene is 50% by weight or more and acrylic acid is An ionic copolymer containing an ethylene-acrylic acid copolymer containing 15% by weight and one or more metal ions dispersed in the copolymer consisting of an α-olefin and an α,β-unsaturated carboxylic acid. The present invention provides a composite film with good heat-sealability, characterized in that a layer obtained by melt-kneading the following is used as a heat-sealing layer. The present invention will be explained in detail below. In the following description, "%" indicating a ratio represents "% by weight". EAA in the present invention is a copolymer containing ethylene and acrylic acid as essential components, and may be copolymerized with other olefins or unsaturated carboxylic acids other than acrylic acid. The copolymerization ratio of ethylene monomer units is 50% or more, and the copolymerization ratio of acrylic acid monomer units is in the range of 3 to 15%. If the acrylic acid content is less than 3%, no improvement in heat sealing properties will be observed, and if it exceeds 15%, the melt viscosity will be too low, resulting in poor moldability. In addition, ionic copolymers containing one or more metal ions dispersed in a copolymer consisting of α-olefin and α,β-unsaturated carboxylic acid (hereinafter referred to as “ionic copolymers”) are Ordinary ionomers can be used, such as partial salts of ethylene-methacrylic acid copolymers with Na ions (Na type) and partial salts with Zn ions (Zn type). In the present invention, it is necessary to melt and knead the above EAA and ionic copolymer, and the mixing ratio of both resins is
EAA95~50%, ionic copolymer 5~50%
A range of 50% is preferred. 5% ionic copolymer
If it is less than 50%, no improvement effect on heat sealing property is observed, and if it exceeds 50%, no improvement effect is seen in spite of the increase, making it uneconomical. The melt-kneading method can be carried out during film formation by various manufacturing methods, but when used as a heat-sealing layer, a coextrusion method with other resins can be suitably applied. In the present invention, remarkable changes in melt index are observed due to melt kneading during film formation, for example, EAA with a melt index of 2.0 and EAA with a melt index of 2.0
When the same amount of ionic copolymer of 2.5 was used and melted and kneaded, the melt index of the resin was 1.5.
It became. Similarly, remarkable changes in the melt viscosity characteristics are seen as shown in FIG. Figure 1 is a graph showing the relationship curve between the apparent viscosity of molten resin and temperature.
40Kg/cm 2 , measured with a nozzle of 1×2 mmφ. Curve A in Figure 1 has a melt index of 7.0.
Curve B (EAA/ionic copolymer = 80/20) and curve C ( EAA/ionic copolymer = 60/40), it can be seen that the viscosity has shifted significantly to the higher viscosity side. The reason for such changes in melt index and melt viscosity is not clear, but it is likely that the metal ions contained in the ionic copolymer have chemical interactions with the acid groups of EAA through heating and melt-kneading. It is thought that this was to wake him up. Next, the present invention will be explained in detail with reference to Examples. (Example) Examples 1 to 4 EAA and ionic copolymer having the resin composition shown in Table 1 were mixed in a mixer at the ratio shown in Table 1, and then subjected to uniaxial extrusion with a diameter of 30 mm and L/D = 25. A film with a thickness of 100 μm was sampled using a T-die. Various physical properties were measured for each film obtained, and the results are shown in Table 1. Comparative Examples 1 to 3 For Comparative Examples 1 and 2, EAA used in the above example was used alone, and Comparative Example 3
Using ordinary low-density polyethylene (LDPE), the same film formation as in the example was carried out, and the physical properties of the obtained film were measured. Physical property measurement method: "MI" measures melt index in accordance with JISK-7210. Similarly, "Haze" is JISK-7105,
and "tensile strength" were measured in accordance with JISK-6761. Regarding "nylon adhesion", each film was made of 60μ thick nylon film (made of 6-nylon).
After temporary adhesion between heated rolls at 100°C, the test pieces were heated and bonded while open (200°C, 1 minute), and the T-peel strength was measured at a tensile speed of 200 mm/min.
【表】
＊ 接着しなかつた為測定不能
表−１から本発明の実施例１〜４のフイルムは
EAAのみからなる比較例１及び２のフイルムに
比べて透明性、引張速度が顕著に改良されてお
り、また、LDPEのみからなる比較例３について
は、透明性、引張強度、ナイロン接着性が全て劣
ることが判る。
実施例 ５，６
インフレーシヨン共押出機を使用し、６−ナイ
ロンを外層、表−２に示す組成物を内層（ヒート
シール層）として、環状口金温度230℃で共押出
成形し、折径550mmの複合フイルムを得た（厚み
は外層25μ、内層40μ）。
なお、実施例５，６に使用したヒートシール層
のEAA、イオン性共重合体は実施例３，４で使
用したものと同一組成である。
得られた複合フイルムのヒートシール強度とホ
ツトタツク性の温度依存性を測定し、その結果を
表−２に示した。
比較例 ４
６ナイロンを外層、実施例５，６で使用した
EAAをヒートシール層として、実施例５，６と
同一の製膜を行ない、得られたフイルムの物性を
測定した。
物性評価及び測定法：
「ヒートシール強度」はヒートシーラーを使用
し、ヒートシールバーの幅10mm、シール圧３Kg／
cm2、シール時間１秒とし、表−２の示すヒートシ
ール温度条件でフイルムのヒートシール層同志を
シールした後、試料幅15mm、引張速度200mm／分
でのＴ型剥離強度を測定した。
「ホツトタツク性」は試料幅30mmとし、上記
「ヒートシール強度」と同一条件でシールを行な
つた直後に、フイルムの片側に200gの荷重をか
けて、ヒートシール層が冷却固化するまでに剥離
が起こつたヒートシール部分の長さを測定した。
この長さが長い程ホツトタツク性に劣る。[Table] * Unable to measure because it did not adhere. From Table 1, the films of Examples 1 to 4 of the present invention were
The transparency and tensile speed were significantly improved compared to the films of Comparative Examples 1 and 2 made only of EAA, and the films of Comparative Example 3 made only of LDPE had all of the transparency, tensile strength, and nylon adhesion. It turns out to be inferior. Examples 5 and 6 Using an inflation coextruder, 6-nylon was used as an outer layer and the composition shown in Table 2 was used as an inner layer (heat seal layer), and coextrusion molding was carried out at an annular die temperature of 230°C. A 550 mm composite film was obtained (thickness: outer layer 25μ, inner layer 40μ). Note that the EAA and ionic copolymer of the heat seal layer used in Examples 5 and 6 had the same composition as those used in Examples 3 and 4. The temperature dependence of the heat-sealing strength and hot-tack properties of the obtained composite film was measured, and the results are shown in Table 2. Comparative Example 4 Nylon 6 was used as the outer layer in Examples 5 and 6.
A film was formed in the same manner as in Examples 5 and 6 using EAA as a heat seal layer, and the physical properties of the obtained film were measured. Physical property evaluation and measurement method: "Heat seal strength" was determined using a heat sealer, heat seal bar width 10 mm, sealing pressure 3 kg/
cm 2 and a sealing time of 1 second, the heat-sealed layers of the film were sealed together under the heat-sealing temperature conditions shown in Table 2, and then the T-peel strength was measured at a sample width of 15 mm and a tensile speed of 200 mm/min. "Hot tackiness" is determined by using a sample width of 30 mm and immediately after sealing under the same conditions as for "heat sealing strength" above, a load of 200 g is applied to one side of the film to ensure that the heat seal layer does not peel off before it cools and solidifies. The length of the heat-sealed portion was measured.
The longer this length is, the worse the hot-tack properties are.
【表】【table】
【表】
−印は未測定
表−２から、本発明の実施例５，６のフイルム
は、ヒートシール層がEAAのみからなる比較例
４と比較すると、低温側のヒートシール強度を維
持しつつ、ホツトタツク性が顕著に改良され、ヒ
ートシール層として優れていることが判る。
（発明の効果）
本発明によれば、各種構成の複合フイルムにお
けるヒートシール層としてEAAを使用でき、そ
の優れた特性により種々の包装分野での利用が図
れる。[Table] − indicates not measured It can be seen that the hot-tack properties are significantly improved and it is excellent as a heat-sealing layer. (Effects of the Invention) According to the present invention, EAA can be used as a heat-sealing layer in composite films of various configurations, and its excellent properties can be used in various packaging fields.
第１図は溶融樹脂の見掛け粘度と温度との関係
曲線を示すグラフである。
FIG. 1 is a graph showing a relationship curve between the apparent viscosity of molten resin and temperature.
Claims (1)
〜15重量％を含むエチレン−アクリル酸共重合体
と、α−オレフイン及びα，β−不飽和カルボン
酸よりなる共重合体中に一種以上の金属イオンを
分散含有しているイオン性共重合体とを溶融混練
してなる層をヒートシール層としたことを特徴と
するヒートシール性良好な複合フイルム。1 Contains 50% or more ethylene and 3% acrylic acid
An ionic copolymer containing one or more metal ions dispersed in a copolymer consisting of an ethylene-acrylic acid copolymer containing ~15% by weight, an α-olefin, and an α,β-unsaturated carboxylic acid. A composite film with good heat-sealability, characterized in that the heat-sealing layer is a layer obtained by melt-kneading the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16733884A JPS6144937A (en) | 1984-08-10 | 1984-08-10 | Modification of ethylene/acrylic acid copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16733884A JPS6144937A (en) | 1984-08-10 | 1984-08-10 | Modification of ethylene/acrylic acid copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6144937A JPS6144937A (en) | 1986-03-04 |
| JPH0460020B2 true JPH0460020B2 (en) | 1992-09-24 |
Family
ID=15847879
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16733884A Granted JPS6144937A (en) | 1984-08-10 | 1984-08-10 | Modification of ethylene/acrylic acid copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6144937A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5547752A (en) * | 1988-06-20 | 1996-08-20 | James River Paper Company, Inc. | Blend of polybutylene and ionomer forming easy-open heatseal |
| US5516847A (en) * | 1991-09-03 | 1996-05-14 | Lisco, Inc. | Golf ball cover having an ionic copolymer/non-ionic copolymer blend |
| US5397840A (en) * | 1991-09-03 | 1995-03-14 | Spalding & Evenflo Companies, Inc. | Golf ball cover having an ionic copolymer/non-ionic copolymer blend |
| US6162852A (en) * | 1996-12-13 | 2000-12-19 | Isolyser Company, Inc. | Degradable polymers |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5034045A (en) * | 1973-07-26 | 1975-04-02 | ||
| JPS5318544A (en) * | 1976-07-30 | 1978-02-20 | Ciba Geigy Ag | Novel phenyl phosphite process for preparing and stabilized organic material composition containing same |
| JPS5670050A (en) * | 1979-10-19 | 1981-06-11 | Du Pont | Elastic terionomer blend |
| JPS5847411A (en) * | 1981-09-14 | 1983-03-19 | 大阪瓦斯株式会社 | Cultivation of horseradish |
-
1984
- 1984-08-10 JP JP16733884A patent/JPS6144937A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5034045A (en) * | 1973-07-26 | 1975-04-02 | ||
| JPS5318544A (en) * | 1976-07-30 | 1978-02-20 | Ciba Geigy Ag | Novel phenyl phosphite process for preparing and stabilized organic material composition containing same |
| JPS5670050A (en) * | 1979-10-19 | 1981-06-11 | Du Pont | Elastic terionomer blend |
| JPS5847411A (en) * | 1981-09-14 | 1983-03-19 | 大阪瓦斯株式会社 | Cultivation of horseradish |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6144937A (en) | 1986-03-04 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |