JPH07195610A - Laminating material - Google Patents
Laminating materialInfo
- Publication number
- JPH07195610A JPH07195610A JP5349854A JP34985493A JPH07195610A JP H07195610 A JPH07195610 A JP H07195610A JP 5349854 A JP5349854 A JP 5349854A JP 34985493 A JP34985493 A JP 34985493A JP H07195610 A JPH07195610 A JP H07195610A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- barrier layer
- polyethylene resin
- intermediate support
- barrier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は積層材に係り、特に、流
動性乃至半流動性物質を収容する、耐内容物保存性に優
れたチューブ容器に用いられる積層材に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated material, and more particularly to a laminated material containing a fluid or semi-fluid substance and used for a tube container excellent in storage stability of contents.
【０００２】[0002]
【従来の技術】練ハミガキ、化粧品、練り食品等のペー
スト状物に代表される流動性乃至半流動性物質を収容す
るチューブ容器は、適度の腰の強さ、耐水性、ガスバリ
アー性等の物性を有する積層材で形成されている筒状の
胴部と、肩部と首部とを有し胴部の上部開口端に係合さ
れている閉塞部材と、この閉塞部材の首部に着脱可能に
装着されているキャップとを備えている。2. Description of the Related Art A tube container containing a fluid or semi-fluid substance represented by a paste-like material such as toothpaste, cosmetics, paste foods, etc., has an appropriate elasticity, water resistance and gas barrier property. A tubular body portion formed of a laminated material having physical properties, a closing member having a shoulder portion and a neck portion and engaged with an upper open end of the body portion, and detachably attached to the neck portion of the closing member. And a cap attached.
【０００３】このようなチューブ容器は、チューブ容器
としての保存特性すなわち収容内容物の浸透に対する耐
デラミ性のあることが要求されている。Such a tube container is required to have storage characteristics as a tube container, that is, delamination resistance against permeation of contained contents.
【０００４】この点から、例えば特開昭６２−６４７４
０号公報では、耐内容物性に優れた保存効果のあるチュ
ーブ容器として、低密度ポリエチレンフィルム／二軸延
伸フィルム／アルミ箔／中〜高密度ポリエチレンフィル
ムの積層構造からなり、各層フィルムがウレタン系接着
剤にて貼り合わせラミネートされてなる、液状シリコン
ゴムが充填されたチューブ容器が提案されている。ま
た、特開平５−７７３５５号公報では、第１バリアー材
の内方に第２の中間バリアー材を形成させることによ
り、内容物の浸透によるデラミ防止を図ったチューブ容
器が提案されている。From this point, for example, Japanese Unexamined Patent Publication No. 62-6474.
In JP-A-0, a tube container having excellent storage resistance and excellent content resistance has a laminated structure of a low density polyethylene film / biaxially stretched film / aluminum foil / medium to high density polyethylene film, and each layer film is a urethane-based adhesive. A tube container filled with liquid silicone rubber, which is formed by laminating and laminating with a chemical, has been proposed. Further, JP-A-5-77355 proposes a tube container in which the second intermediate barrier material is formed inside the first barrier material to prevent delamination due to the permeation of the contents.
【０００５】ところでチューブ容器においては、保存性
に優れることと同時に、チューブ容器としての耐圧強度
が安定していることが当然に必要な物性である。チュー
ブ容器は、例えば特開昭６３−５５０６３号公報に開示
されているように、一般に、積層材の１側辺部端面と他
側辺部とを重ね合わさせ、熱溶接して胴部を接合するこ
とによって形成される。チューブ容器の包材強度は、こ
の重ね合わせ部分における接着強度が最も弱く、一般に
は耐圧強度の他、重ね合わせ接着部の引っ張り強度とし
て表現されるものであり、かかる層間強度の強さも要求
される。By the way, it is a necessary physical property for the tube container to have excellent storability and stable pressure resistance as a tube container. In a tube container, as disclosed in, for example, Japanese Patent Laid-Open No. 63-55063, generally, the end face of one side portion and the other side portion of the laminated material are overlapped and heat-welded to join the body portion. Formed by. The packaging material strength of the tube container has the weakest adhesive strength in the overlapping portion, and is generally expressed as tensile strength of the overlapping adhesion portion in addition to pressure resistance strength, and strength of such interlayer strength is also required. .
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、上記従
来例において、例えば特開昭６２−６４７４０号のよう
に中〜高密度ポリエチレンフィルムを最内層側に配した
場合、該チューブ容器にハック油や鉱物油、炭化水素系
ワックス等の浸透性成分を含有する内容物を充填した際
に、これらの成分が最内層フィルムを浸透し、接着剤を
膨潤可塑化させ、デラミ、破袋に至る例がみられるとい
う不具合があった。また、特開平５−７７３５５号に示
す容器においては、保存効果は高められるものの、製造
コストが高くなるという問題があった。However, in the above-mentioned conventional example, when a medium to high density polyethylene film is arranged on the innermost layer side as in JP-A-62-64740, hack oil and minerals are placed in the tube container. When filling contents containing penetrating components such as oil and hydrocarbon wax, these components permeate the innermost layer film and swell and plasticize the adhesive, resulting in delamination and bag breaking. There was a problem that it could be. Further, in the container disclosed in JP-A-5-77355, the storage effect is enhanced, but the production cost is high.
【０００７】本発明は、このような事情に鑑みてなされ
たものであり、層間の強度が強く、耐内容物保存性に優
れたチューブ容器に用いられる積層材を安価に提供する
ことを目的とする。The present invention has been made in view of the above circumstances, and an object thereof is to provide a laminated material used for a tube container having high strength between layers and excellent in storage stability of contents at low cost. To do.
【０００８】[0008]
【課題を解決するための手段】かかる目的を達成するた
めの本発明の構成は、二軸延伸樹脂フィルムからなる中
間支持層と、該中間支持層の内側に形成されたバリアー
層と、該中間支持層の外側に位置し熱可塑性樹脂層から
なる最外層と、前記バリアー層の内側に位置し密度０．
９２〜０．９５の直鎖型ポリエチレン樹脂からなる最内
層とを備え、さらに該最内層と前記バリアー層との間に
バリアー層側から順に酸コポリマー層と低密度ポリエチ
レン樹脂層とを備えることを特徴とする積層材である。Means for Solving the Problems The constitution of the present invention for achieving the above object is to provide an intermediate support layer made of a biaxially stretched resin film, a barrier layer formed inside the intermediate support layer, and an intermediate support layer. The outermost layer made of a thermoplastic resin layer is located outside the supporting layer, and the density is 0.
92-0.95 innermost layer made of a linear polyethylene resin, and further comprising an acid copolymer layer and a low-density polyethylene resin layer between the innermost layer and the barrier layer in order from the barrier layer side. It is a characteristic laminated material.
【０００９】上記最内層をなす直鎖型ポリエチレンは、
エチレン−αオレフィン共重合体で、αオレフィンとし
てＣ3 〜Ｃ8 、密度としてｄ＝０．９２〜０．９５のポ
リエチレンを示す。The linear polyethylene forming the innermost layer is
This is an ethylene-α-olefin copolymer, and polyethylene having C 3 to C 8 as the α olefin and d = 0.92 to 0.95 as the density is shown.
【００１０】なお、上記バリアー層は金属箔あるいは金
属薄膜層であるのが好ましく、金属としてはアルミニウ
ムが特に好ましい。The barrier layer is preferably a metal foil or a metal thin film layer, and aluminum is particularly preferable as the metal.
【００１１】[0011]
【作用】バリアー層（軟質アルミニウム箔）と密度０．
９２〜０．９５の直鎖型ポリエチレン樹脂層からなる最
内層の間に、バリアー層側から順に酸コポリマー層と低
密度ポリエチレン樹脂層とを備えることにより、バリア
ー層と酸コポリマー層との間では金属−カルボン酸の水
素結合によって層間強度が高められ、これにより接着安
定化が得られ、また、低密度ポリエチレン樹脂層を介在
させることによって、本来それぞれの樹脂の相溶性、流
動性の差から層間強度が弱く、接着性の良好でない酸コ
ポリマー層と最内層（直鎖型ポリエチレン樹脂）との間
の安定化が確保され、デラミの発生防止が図られる。さ
らに、最内層を直鎖低密度ポリエチレン樹脂層とするこ
とにより、高浸透性成分を含有する内容物を収容した場
合でも高い耐浸透性を得ることができ、内容物保存性が
図られる。Function: Barrier layer (soft aluminum foil) and density of 0.
By providing the acid copolymer layer and the low-density polyethylene resin layer in this order from the barrier layer side between the innermost layer of the linear polyethylene resin layer of 92 to 0.95, the barrier layer and the acid copolymer layer are provided between the barrier layer and the acid copolymer layer. The hydrogen bond between the metal and the carboxylic acid enhances the interlayer strength, which results in the stabilization of the adhesion, and the interposition of the low-density polyethylene resin layer originally results in the difference in the compatibility and fluidity of the respective resins, resulting in the interlayer Stabilization is ensured between the acid copolymer layer having weak strength and poor adhesiveness and the innermost layer (straight-chain polyethylene resin), and delamination is prevented. Further, by forming the linear low-density polyethylene resin layer as the innermost layer, high penetration resistance can be obtained even when a content containing a high-penetration component is stored, and the storage stability of the content can be achieved.
【００１２】[0012]
【実施例】以下、本発明の好適な実施例について図面を
参照しながら説明する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT A preferred embodiment of the present invention will be described below with reference to the drawings.
【００１３】図１は本発明の積層材の概略断面図であ
る。図１において、本発明の積層材１は、二軸延伸樹脂
フィルムからなる中間支持層２と、該中間支持層の内側
（図面下方）に形成されたバリアー層３と、該中間支持
層の外側（図面上方）に位置し熱可塑性樹脂層からなる
最外層４と、前記バリアー層の内側に位置し密度０．９
２〜０．９５の直鎖型ポリエチレン樹脂からなる最内層
５とを備え、さらに該最内層５と前記バリアー層３との
間にバリアー層側から順に酸コポリマー層６と低密度ポ
リエチレン樹脂層７とを有している。FIG. 1 is a schematic sectional view of the laminated material of the present invention. In FIG. 1, the laminated material 1 of the present invention comprises an intermediate support layer 2 made of a biaxially stretched resin film, a barrier layer 3 formed inside the intermediate support layer (downward in the drawing), and outside the intermediate support layer. The outermost layer 4 made of a thermoplastic resin layer (above the drawing) and having a density of 0.9 at the inside of the barrier layer.
2 to 0.95 innermost layer 5 made of a linear polyethylene resin, and between the innermost layer 5 and the barrier layer 3, the acid copolymer layer 6 and the low-density polyethylene resin layer 7 are arranged in this order from the barrier layer side. And have.
【００１４】中間支持層２は、チューブ容器の寸法安定
化を図るためのもので、これに用いられる２軸延伸樹脂
フィルムとしては、ポリエチレンテレフタレート、ポリ
プロピレン、ポリエステル、ナイロン、エチレン−ビニ
ルアルコール共重合体等の透明フィルムあるいは半透明
フィルムを挙げることができる。このような２軸延伸フ
ィルムの厚さは１０〜５０μｍ程度が好ましい。また、
中間支持層２によるバリアー性向上のために、２軸延伸
樹脂フィルムの表面にポリ塩化ビニリデン等を塗布して
もよい。また、グラビア印刷、オフセット印刷等の公知
の印刷方式による印刷化粧加工を施してもよい。The intermediate support layer 2 is for stabilizing the dimension of the tube container, and the biaxially stretched resin film used for this is polyethylene terephthalate, polypropylene, polyester, nylon, ethylene-vinyl alcohol copolymer. And transparent films or translucent films. The thickness of such a biaxially stretched film is preferably about 10 to 50 μm. Also,
In order to improve the barrier property of the intermediate support layer 2, polyvinylidene chloride or the like may be applied to the surface of the biaxially stretched resin film. In addition, print makeup processing may be performed by a known printing method such as gravure printing or offset printing.
【００１５】中間支持層２の内側に積層されるバリアー
層３としては、好適には軟質アルミニウム、銅、鉄、ニ
ッケル等の金属箔により形成することができるが、特に
は軟質アルミニウム箔が最も好適に用いられる。このバ
リアー層３の厚さは、十分なバリアー性を得るために６
〜５０μｍ程度が好ましい。The barrier layer 3 laminated on the inner side of the intermediate support layer 2 can be preferably formed of a metal foil of soft aluminum, copper, iron, nickel or the like, but a soft aluminum foil is most preferred. Used for. The thickness of the barrier layer 3 is 6 in order to obtain sufficient barrier properties.
It is preferably about 50 μm.
【００１６】中間支持層２の外側に位置する最外層４
は、熱可塑性樹脂層からなり、図２に示すように、積層
材１を筒状にしてチューブ容器の胴部を形成する際に、
その最外層４の表面４ａが後述の最内層（直鎖型ポリエ
チレン樹脂層）５の表面５ａと辺縁部にて重ね合わされ
て熱融着されるものであることから、ヒートシール性が
要求され、低密度ポリエチレン、直鎖型ポリエチレン、
ポリプロピレン、中密度ポリエチレン、高密度ポリエチ
レン、エチレン−酢酸ビニル共重合体、エチレン−アク
リル酸共重合体、エチレン−メタクリル酸共重合体、ア
イオノマー、ポリプロピレン、エチレン−ビニルアルコ
ール共重合体、ポリアミド、ポリエステル、ポリアクリ
ロニトリル等の少なくとも一種以上の熱可塑性樹脂から
なる。このような最外層４の厚さは３０〜２００μｍ程
度であることが好ましい。The outermost layer 4 located outside the intermediate support layer 2
Is composed of a thermoplastic resin layer, and as shown in FIG. 2, when the laminated material 1 is formed into a tubular shape to form the body of the tube container,
Since the surface 4a of the outermost layer 4 and the surface 5a of the innermost layer (straight-chain polyethylene resin layer) 5 which will be described later are overlapped and heat-sealed at the peripheral portion, heat sealability is required. , Low density polyethylene, linear polyethylene,
Polypropylene, medium density polyethylene, high density polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ionomer, polypropylene, ethylene-vinyl alcohol copolymer, polyamide, polyester, It is made of at least one kind of thermoplastic resin such as polyacrylonitrile. The thickness of such outermost layer 4 is preferably about 30 to 200 μm.
【００１７】これら最外層４、中間支持層２およびバリ
アー層３の各層は、低密度ポリエチレンによる押出しラ
ミネーション、ウレタン系接着剤によるドライラミネー
ション等の公知の方法により貼り合わせられ、積層され
る。The outermost layer 4, the intermediate support layer 2 and the barrier layer 3 are laminated and laminated by a known method such as extrusion lamination with low density polyethylene and dry lamination with urethane adhesive.
【００１８】前記バリアー層３の内側に位置する最内層
５は、本発明においては密度０．９２〜０．９５の直鎖
型ポリエチレン樹脂（ＬＬＤＰＥ）からなり、これによ
り、チューブ容器内に収容される内容物が例えば香料、
鉱物油、有機系極性溶剤等の浸透性の高い物質を含有す
る場合でも、該内容物の浸透性抑制を図ることができ、
保存特性に優れた積層材１を得ることができる。またこ
の直鎖低密度ポリエチレン樹脂はヒートシール性を有し
ていることから、前述したように積層材１を筒状にして
チューブ容器の胴部を形成する際に、この最内層５の表
面５ａが最外層４の表面４ａと辺縁部にて重ね合わされ
て熱融着されるが、このとき確実にしかも安定してヒー
トシールされることができる。この最内層５は、エチレ
ン−αオレフィン共重合体で、αオレフィンとしてＣ3
〜Ｃ8 、密度としてｄ＝０．９２〜０．９５のポリエチ
レンであり、特には密度０．９２５〜０．９４程度が好
ましく、厚さは３０〜２００μｍ程度であることが好ま
しい。The innermost layer 5 located inside the barrier layer 3 is made of a linear polyethylene resin (LLDPE) having a density of 0.92 to 0.95 in the present invention, and is thereby housed in a tube container. The contents are, for example, fragrance,
Even when containing a highly permeable substance such as mineral oil and organic polar solvent, it is possible to suppress the permeability of the content,
The laminated material 1 having excellent storage characteristics can be obtained. Since this linear low-density polyethylene resin has a heat-sealing property, the surface 5a of the innermost layer 5 is formed when the laminated material 1 is formed into a tubular shape to form the body of the tube container as described above. Is superposed on the surface 4a of the outermost layer 4 at the peripheral portion and heat-sealed, but at this time, it can be reliably and stably heat-sealed. The innermost layer 5 is an ethylene-α-olefin copolymer, and has C 3 as an α-olefin.
-C 8 and polyethylene having a density d = 0.92 to 0.95, particularly preferably a density of about 0.925 to 0.94, and a thickness of about 30 to 200 μm.
【００１９】最内層５と前記バリアー層３との間には、
両者間の接着性の安定化を図るために、バリアー層側か
ら順に酸コポリマー層６と低密度ポリエチレン樹脂層７
とが積層されている。Between the innermost layer 5 and the barrier layer 3,
In order to stabilize the adhesiveness between the two, the acid copolymer layer 6 and the low-density polyethylene resin layer 7 are sequentially arranged from the barrier layer side.
And are stacked.
【００２０】酸コポリマー層６は、バリアー層（アルミ
箔）３との間の接着性の安定化を図りデラミを防止する
ためのもので、例えばエチレン−メタクリル酸共重合体
（ＥＭＡＡ）、エチレン−アクリル酸共重合体（ＥＡ
Ａ）等を挙げられるが、特にはアクリル酸濃度４〜１５
％程度のエチレン−アクリル酸共重合体が好ましい。酸
コポリマー層６とバリアー層（アルミ箔）３とは、カル
ボン酸−金属間の水素結合によって層間強度が高めら
れ、これにより接着安定化が得られる。この酸コポリマ
ー層６は、バリアー層（アルミ箔）３に対して押出しラ
ミネーション、熱ラミネーションなどによって積層さ
れ、厚さは１０〜５０μｍ程度が好ましい。The acid copolymer layer 6 is intended to stabilize the adhesiveness with the barrier layer (aluminum foil) 3 and prevent delamination, and for example, ethylene-methacrylic acid copolymer (EMAA), ethylene- Acrylic acid copolymer (EA
A) and the like, but especially acrylic acid concentration 4 to 15
% Ethylene-acrylic acid copolymer is preferred. The acid copolymer layer 6 and the barrier layer (aluminum foil) 3 have increased interlaminar strength due to carboxylic acid-metal hydrogen bond, and thus, stabilization of adhesion can be obtained. The acid copolymer layer 6 is laminated on the barrier layer (aluminum foil) 3 by extrusion lamination, thermal lamination, or the like, and preferably has a thickness of about 10 to 50 μm.
【００２１】低密度ポリエチレン樹脂（ＬＤＰＥ）層７
は、直鎖型ポリエチレン樹脂からなる最内層５を形成さ
せるための中間のサンドポリエチレン樹脂層として使用
され、この低密度ポリエチレン樹脂層７を介在させるこ
とによって、本来それぞれの樹脂の相溶性、流動性の差
から層間強度が弱く、接着性の良好でない酸コポリマー
層６と最内層５との間の安定化を確保し、デラミの発生
防止を図るものである。前記酸コポリマー層６と最内層
５とは、この低密度ポリエチレン樹脂層７により押出し
ラミネーションすることによって積層される。この低密
度ポリエチレン樹脂層７は、上記機能を効果的に発揮さ
せるためには密度０．９１〜０．９３程度が好ましく、
厚さは１０〜５０μｍ程度が好ましい。Low density polyethylene resin (LDPE) layer 7
Is used as an intermediate sand polyethylene resin layer for forming the innermost layer 5 made of a linear polyethylene resin, and by interposing this low density polyethylene resin layer 7, the compatibility and fluidity of the respective resins are originally intended. The difference between the two is that the interlayer strength is weak and the adhesion between the acid copolymer layer 6 and the innermost layer 5, which does not have good adhesiveness, is secured, and delamination is prevented. The acid copolymer layer 6 and the innermost layer 5 are laminated by extrusion lamination with the low density polyethylene resin layer 7. The low density polyethylene resin layer 7 preferably has a density of about 0.91 to 0.93 in order to effectively exhibit the above functions,
The thickness is preferably about 10 to 50 μm.
【００２２】以上のようにして得られる本発明に係る積
層材１は、例えば打ち抜き加工してチューブ容器胴部用
成形用のブランク板を得た後、該ブランク板の縁辺部を
一方の最内層５の表面５ａを他方の最外層４の表面４ａ
上に重畳させ、熱融着して容器胴部を形成した後、所要
の工程を経てチューブ容器を得る。 （実験例）次に実験例を挙げて本発明を更に具体的に説
明する。試料１ 図１に示される積層構成の積層材を以下のようにして作
成した。The laminated material 1 according to the present invention obtained as described above is, for example, punched to obtain a blank plate for forming a tube container body, and then the edge of the blank plate is used as one innermost layer. Surface 5a of the other outermost layer 4
After being superposed and heat-sealed to form a container body, a tube container is obtained through the required steps. (Experimental example) Next, the present invention will be described in more detail with reference to experimental examples. Sample 1 A laminated material having a laminated constitution shown in FIG. 1 was prepared as follows.
【００２３】まず、最外層フィルムとして厚さ５０μｍ
の中密度ポリエチレンフィルム（大日本樹脂（株）製
ＭＰＡ、密度０．９３５）を、中間支持層として厚さ１
２μｍの２軸延伸ポリエチレンテレフタレートフィルム
（東洋紡（株）製 Ｔ４１００）を、バリアー層として
厚さ９μｍの軟質アルミニウム箔（東海アルミ（株）
製）をそれぞれ用意し、各層をウレタン系接着剤（武田
薬品（株）製 Ａ５１５／Ａ１２）５ｇ／ｍ2 （乾燥
時）にてドライラミネートし、中密度ポリエチレンフィ
ルム／２軸延伸ポリエチレンテレフタレートフィルム／
軟質アルミニウム箔の３層積層体を作成した。First, the outermost layer film has a thickness of 50 μm.
Medium density polyethylene film (manufactured by Dainippon Plastics Co., Ltd.)
MPA, density 0.935) as an intermediate support layer with a thickness of 1
A 2 μm biaxially stretched polyethylene terephthalate film (T4100 manufactured by Toyobo Co., Ltd.) was used as a barrier layer to form a soft aluminum foil with a thickness of 9 μm (Tokai Aluminum Co., Ltd.).
Each), and each layer is dry laminated with a urethane adhesive (A515 / A12 manufactured by Takeda Pharmaceutical Co., Ltd.) 5 g / m 2 (when dry) to obtain a medium density polyethylene film / biaxially stretched polyethylene terephthalate film /
A three-layer laminate of soft aluminum foil was created.
【００２４】次に、上記積層体の軟質アルミニウム箔面
上に、厚さ３０μｍのエチレン−メタクリル酸共重合体
（ＥＭＡＡ）樹脂フィルム（三井石油化学（株）製 Ｎ
１１０８Ｃ、アクリル酸濃度１１％）を押出しラミネー
トし、さらに、このエチレン−メタクリル酸共重合体樹
脂面に対し、厚さ２０μｍの低密度ポリエチレン（三井
石油化学（株）製 Ｍ１１Ｐ、密度０．９１７）を押出
しラミネートすることにより、厚さ２００μｍの直鎖型
ポリエチレン樹脂フィルム（大日本樹脂（株）製 ＳＲ
Ｘ、密度０．９２）をサンドラミネートして本発明に係
る積層材（試料１）を得た。比較試料１ 試料１において、３層積層体の軟質アルミニウム箔面上
に対し、厚さ３０μｍのエチレン−メタクリル酸共重合
体樹脂フィルム（三井石油化学（株）製 Ｎ１１０８
Ｃ、アクリル酸濃度１１％）を押出しラミネートして、
低密度ポリエチレンフィルムを介在させることなく、厚
さ２００μｍの直鎖型ポリエチレン樹脂フィルム（大日
本樹脂（株）製 ＳＲＸ、密度０．９２）をサンドラミ
ネートした以外は試料１と同様にして積層材（比較試料
１）を得た。比較試料２ 試料１において、３層積層体の軟質アルミニウム箔面上
に対し、エチレン−メタクリル酸共重合体樹脂フィルム
を介在させることなく、厚さ２０μｍの低密度ポリエチ
レン樹脂フィルム（三井石油化学（株）製 Ｍ１１Ｐ、
密度０．９１７）を押出しラミネートすることにより、
厚さ２００μｍの直鎖型低密度ポリエチレン樹脂フィル
ム（大日本樹脂（株）製 ＳＲＸ、密度０．９２）をサ
ンドラミネートした以外は試料１と同様にして積層材
（比較試料２）を得た。比較試料３ 試料１において、３層積層体の軟質アルミニウム箔面上
に対し、ウレタン系アンカーコート剤（武田薬品（株）
製 Ａ３１０／Ａ１２）を用いてアンカーコート層を形
成し、このアンカーコート層上に３０μｍの厚さで押出
した低密度ポリエチレン樹脂（三井石油化学（株）製
Ｍ１１Ｐ、密度０．９１７）を介して、最内層の直鎖型
ポリエチレン樹脂フィルムを押出しラミネートすること
によって、厚さ２００μｍの直鎖型ポリエチレン樹脂フ
ィルム（大日本樹脂（株）製 ＳＲＸ、密度０．９２
０）をサンドラミネートした以外は試料１と同様にして
比較例の積層材（比較試料３）を得た。比較試料４ 試料１において、最内層を直鎖型ポリエチレン樹脂フィ
ルムに代えて、厚さ２００μｍの低密度ポリエチレン樹
脂フィルム（大日本樹脂（株）製 Ｍ１６Ｐ、密度０．
９２３）とした以外は試料１と同様にして積層材（比較
試料４）を得た。比較試料５ 試料１において、エチレン−アクリル酸共重合体樹脂層
の内側に形成される層ムを、低密度ポリエチレン樹脂に
代えて、厚さ２０μｍの中密度ポリエチレン樹脂（三井
石油化学（株）製 Ｃ−２６０−４Ｐ、密度０．９３
２）とした以外は試料１と同様にして積層材（比較試料
５）を得た。Next, an ethylene-methacrylic acid copolymer (EMAA) resin film (Mitsui Petrochemical Co., Ltd. N) having a thickness of 30 μm was formed on the soft aluminum foil surface of the laminate.
1108C, acrylic acid concentration 11%) was extruded and laminated, and 20 μm thick low-density polyethylene (M11P manufactured by Mitsui Petrochemical Co., Ltd., density 0.917) was further applied to the ethylene-methacrylic acid copolymer resin surface. 200 μm thick linear polyethylene resin film (SR from Dainippon Resin Co., Ltd. SR
X and a density of 0.92) were sand-laminated to obtain a laminated material (Sample 1) according to the present invention. Comparative Sample 1 In Sample 1, an ethylene-methacrylic acid copolymer resin film (N1108 manufactured by Mitsui Petrochemical Co., Ltd.) having a thickness of 30 μm was formed on the soft aluminum foil surface of the three-layer laminate.
C, acrylic acid concentration 11%) is extruded and laminated,
Laminated material was prepared in the same manner as Sample 1 except that a linear polyethylene resin film having a thickness of 200 μm (SRX manufactured by Dainippon Resin Co., Ltd., density 0.92) was sand laminated without interposing a low density polyethylene film ( Comparative sample 1) was obtained. Comparative Sample 2 In Sample 1, a low-density polyethylene resin film having a thickness of 20 μm was formed on the soft aluminum foil surface of the three-layer laminate without interposing an ethylene-methacrylic acid copolymer resin film (Mitsui Petrochemical Co., Ltd. ) Made of M11P,
By extruding and laminating the density 0.917),
A laminated material (comparative sample 2) was obtained in the same manner as in sample 1 except that a linear low-density polyethylene resin film (SRX manufactured by Dainippon Resin Co., Ltd., density 0.92) having a thickness of 200 μm was sand laminated. Comparative Sample 3 In Sample 1, a urethane-based anchor coating agent (Takeda Yakuhin Co., Ltd.) was applied to the soft aluminum foil surface of the three-layer laminate.
A310 / A12 manufactured by Mitsui Chemical Co., Ltd. is used to form an anchor coat layer, and a low density polyethylene resin (manufactured by Mitsui Petrochemical Co., Ltd.) extruded on the anchor coat layer to a thickness of 30 μm.
The linear polyethylene resin film of the innermost layer is extruded and laminated via M11P, density 0.917) to form a linear polyethylene resin film having a thickness of 200 μm (manufactured by Dainippon Resin Co., Ltd., SRX, density 0. 92
A laminated material of Comparative Example (Comparative Sample 3) was obtained in the same manner as Sample 1 except that (0) was sand laminated. Comparative Sample 4 In Sample 1, the innermost layer was replaced with a linear polyethylene resin film, and a low-density polyethylene resin film having a thickness of 200 μm (M16P manufactured by Dainippon Resin Co., Ltd., density 0.
A laminated material (Comparative Sample 4) was obtained in the same manner as in Sample 1 except that the above-mentioned was used. Comparative Sample 5 In Sample 1, the layer formed inside the ethylene-acrylic acid copolymer resin layer was replaced with a low-density polyethylene resin, and a 20 μm thick medium-density polyethylene resin (manufactured by Mitsui Petrochemical Co., Ltd.) was used. C-260-4P, density 0.93
A laminated material (Comparative Sample 5) was obtained in the same manner as in Sample 1 except that the above was used.
【００２５】このようにして作成した試料１、比較試料
１〜５の積層材をそれぞれ打ち抜き加工してチューブ容
器胴部用成形用のブランク板を得た後、該ブランク板の
側辺部を一方の最内層を他方の最外層上に重畳させ、ヒ
ートシールして容器胴部を形成した後、チューブ容器を
成形成した。そして、これら各容器に５％ハッカ油を含
有するグリセリン溶液１００ｃｃを充填し、４０℃にて
オーブン内に容器を静置し、保存後１か月目、３か月目
における容器の保存特性を調べた。The laminated materials of Sample 1 and Comparative Samples 1 to 5 prepared in this way were punched to obtain blank plates for forming the body of the tube container, and one side portion of the blank plates was used. The innermost layer of was laminated on the other outermost layer and heat-sealed to form a container body, and then a tube container was formed. Then, each of these containers was filled with 100 cc of glycerin solution containing 5% peppermint oil, and the containers were allowed to stand in an oven at 40 ° C. Examined.
【００２６】その結果、試料１では、保存後１か月目で
は全く異常がみられず、保存後３か月目でも異常がみら
れなかった。As a result, in Sample 1, no abnormality was observed at 1 month after storage, and no abnormality was observed at 3 months after storage.
【００２７】一方、比較試料１〜３では、保存後１か月
目でそれぞれ、ＥＭＡＡ−ＬＬＤＰＥ間でデラミ発生
（比較試料１）、軟質Ａｌ−ＬＤＰＥ間でデラミ発生
（比較試料２）、軟質Ａｌ−ＬＤＰＥ間でデラミ発生
（比較試料３）がみられた。また、比較試料４では、保
存後１か月目では異常がみられなかったが、保存後２か
月目で軟質Ａｌ−ＥＭＡＡ間にデラミ発生がみられた。
比較試料５では、保存後１か月目でＡｌ−中密度ＰＥ間
でデラミが発生した。On the other hand, in Comparative Samples 1 to 3, delamination occurred between EMAA-LLDPE (Comparative Sample 1), soft Al-LDPE occurred (Comparative Sample 2), and soft Al in the first month after storage. -Delamination occurred between LDPE (Comparative Sample 3). Further, in Comparative Sample 4, no abnormality was observed 1 month after storage, but delamination was observed between the soft Al-EMAA 2 months after storage.
In Comparative Sample 5, delamination occurred between Al and medium density PE one month after storage.
【００２８】[0028]
【効果】以上のように本発明の積層材は、二軸延伸樹脂
フィルムからなる中間支持層と、該中間支持層の内側に
形成されたバリアー層と、該中間支持層の外側に位置し
熱可塑性樹脂層からなる最外層と、前記バリアー層の内
側に位置し直鎖低密度ポリエチレン樹脂からなる最内層
とを備え、さらに該最内層と前記バリアー層との間にバ
リアー層側から順に酸コポリマー層と低密度ポリエチレ
ン樹脂層とを備えているので、浸透抑制効果のある、耐
内容物保存性に優れたチューブ容器に用いられる積層材
を安価に提供することができるという効果を奏する。[Effect] As described above, the laminated material of the present invention has an intermediate support layer formed of a biaxially stretched resin film, a barrier layer formed inside the intermediate support layer, and a heat layer positioned outside the intermediate support layer. An outermost layer made of a plastic resin layer and an innermost layer made of a linear low-density polyethylene resin located inside the barrier layer are provided, and the acid copolymer is further provided between the innermost layer and the barrier layer from the barrier layer side. Since the layer and the low-density polyethylene resin layer are provided, it is possible to inexpensively provide a laminated material that is used for a tube container that has an effect of suppressing permeation and is excellent in storage stability of contents.
【図１】本発明の積層材の一実施例を示す概略断面図で
ある。FIG. 1 is a schematic cross-sectional view showing an example of a laminated material of the present invention.
【図２】本発明の積層材を用いてチューブ容器胴部を形
成する際の積層材辺縁部におけるシール状態を示す説明
図である。FIG. 2 is an explanatory view showing a sealing state at a peripheral portion of a laminated material when a tube container body is formed using the laminated material of the present invention.
１… 積層材 ２… 二軸延伸フィルムからなる中間支持層 ３… バリアー層 ４… 熱可塑性樹脂層からなる最外層 ４ａ…最外層の表面 ５… 直鎖型ポリエチレン樹脂層からなる最内層 ５ａ…最内層の表面 ６… 酸コポリマー層 ７… 低密度ポリエチレン樹脂層 DESCRIPTION OF SYMBOLS 1 ... Laminated material 2 ... Intermediate support layer consisting of biaxially stretched film 3 ... Barrier layer 4 ... Outermost layer consisting of thermoplastic resin layer 4a ... Surface of outermost layer 5 ... Innermost layer 5a consisting of linear polyethylene resin layer 5a ... Surface of inner layer 6 ... Acid copolymer layer 7 ... Low density polyethylene resin layer
Claims (3)
層と、該中間支持層の内側に形成されたバリアー層と、
該中間支持層の外側に位置し熱可塑性樹脂層からなる最
外層と、前記バリアー層の内側に位置し、密度０．９２
〜０．９５の直鎖型ポリエチレン樹脂からなる最内層と
を備え、さらに該最内層と前記バリアー層との間にバリ
アー層側から順に酸コポリマー層と低密度ポリエチレン
樹脂層とを備えることを特徴とする積層材。1. An intermediate support layer made of a biaxially stretched resin film, and a barrier layer formed inside the intermediate support layer,
The outermost layer made of a thermoplastic resin layer is located outside the intermediate support layer, and is located inside the barrier layer, and has a density of 0.92.
To 0.95 of an innermost layer made of a linear polyethylene resin, and further comprising an acid copolymer layer and a low density polyethylene resin layer between the innermost layer and the barrier layer in order from the barrier layer side. And laminated material.
膜層であることを特徴とする請求項１記載の積層材。2. The laminated material according to claim 1, wherein the barrier layer is a metal foil or a metal thin film layer.
属がアルミニウムであることを特徴とする請求項１記載
の積層材。3. The laminated material according to claim 1, wherein the metal forming the metal foil or the metal thin film layer is aluminum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34985493A JP3258800B2 (en) | 1993-12-30 | 1993-12-30 | Laminated material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34985493A JP3258800B2 (en) | 1993-12-30 | 1993-12-30 | Laminated material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07195610A true JPH07195610A (en) | 1995-08-01 |
| JP3258800B2 JP3258800B2 (en) | 2002-02-18 |
Family
ID=18406574
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34985493A Expired - Fee Related JP3258800B2 (en) | 1993-12-30 | 1993-12-30 | Laminated material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3258800B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100390026C (en) * | 2004-10-15 | 2008-05-28 | 甘国工 | Packaging bag combined bi-directional drawn cylindrical shaped membrane with not drawn cylindrical shaped membrane, and production method |
| JP2009248457A (en) * | 2008-04-07 | 2009-10-29 | Dainippon Printing Co Ltd | Laminate sheet for forming laminate tube body part and laminate tube |
| JP2010137886A (en) * | 2008-12-11 | 2010-06-24 | Dainippon Printing Co Ltd | Laminate tube |
| JP2010222711A (en) * | 2009-03-19 | 2010-10-07 | Kao Corp | Packed softener |
| JP2017222138A (en) * | 2016-06-17 | 2017-12-21 | 共同印刷株式会社 | Laminate and tube container |
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|---|---|---|---|---|
| JPS5869043A (en) * | 1981-09-29 | 1983-04-25 | アメリカン・ナショナル・キャン・カンパニー | Multilayer sheet material and flexible slight take-out tube |
| JPS59198143A (en) * | 1983-04-05 | 1984-11-09 | アメリカン・カン・カンパニ− | Multilayer flexible sheet structure |
| JPS6264740A (en) * | 1985-09-17 | 1987-03-23 | 東芝シリコ−ン株式会社 | Tubular vessel filled with liquefied silicone rubber |
| JPS62169635A (en) * | 1986-01-22 | 1987-07-25 | 関西チユ−ブ株式会社 | Raw fabric for laminated tube |
| JPH03153346A (en) * | 1989-11-10 | 1991-07-01 | Sun A Chem Ind Co Ltd | Raw sheet for laminated tube |
| JPH0463236U (en) * | 1990-10-04 | 1992-05-29 | ||
| JPH04201332A (en) * | 1990-11-30 | 1992-07-22 | Dainippon Printing Co Ltd | Laminated material |
| JPH0577355A (en) * | 1991-07-18 | 1993-03-30 | Dainippon Printing Co Ltd | Laminated sheet for forming body part of tube container |
| JPH0891396A (en) * | 1993-11-08 | 1996-04-09 | Toppan Printing Co Ltd | Laminated tube container and its manufacturing method |
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1993
- 1993-12-30 JP JP34985493A patent/JP3258800B2/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5869043A (en) * | 1981-09-29 | 1983-04-25 | アメリカン・ナショナル・キャン・カンパニー | Multilayer sheet material and flexible slight take-out tube |
| JPS59198143A (en) * | 1983-04-05 | 1984-11-09 | アメリカン・カン・カンパニ− | Multilayer flexible sheet structure |
| JPS6264740A (en) * | 1985-09-17 | 1987-03-23 | 東芝シリコ−ン株式会社 | Tubular vessel filled with liquefied silicone rubber |
| JPS62169635A (en) * | 1986-01-22 | 1987-07-25 | 関西チユ−ブ株式会社 | Raw fabric for laminated tube |
| JPH03153346A (en) * | 1989-11-10 | 1991-07-01 | Sun A Chem Ind Co Ltd | Raw sheet for laminated tube |
| JPH0463236U (en) * | 1990-10-04 | 1992-05-29 | ||
| JPH04201332A (en) * | 1990-11-30 | 1992-07-22 | Dainippon Printing Co Ltd | Laminated material |
| JPH0577355A (en) * | 1991-07-18 | 1993-03-30 | Dainippon Printing Co Ltd | Laminated sheet for forming body part of tube container |
| JPH0891396A (en) * | 1993-11-08 | 1996-04-09 | Toppan Printing Co Ltd | Laminated tube container and its manufacturing method |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100390026C (en) * | 2004-10-15 | 2008-05-28 | 甘国工 | Packaging bag combined bi-directional drawn cylindrical shaped membrane with not drawn cylindrical shaped membrane, and production method |
| JP2009248457A (en) * | 2008-04-07 | 2009-10-29 | Dainippon Printing Co Ltd | Laminate sheet for forming laminate tube body part and laminate tube |
| JP2010137886A (en) * | 2008-12-11 | 2010-06-24 | Dainippon Printing Co Ltd | Laminate tube |
| JP2010222711A (en) * | 2009-03-19 | 2010-10-07 | Kao Corp | Packed softener |
| JP2017222138A (en) * | 2016-06-17 | 2017-12-21 | 共同印刷株式会社 | Laminate and tube container |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3258800B2 (en) | 2002-02-18 |
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