JPH01139347A - Tube container - Google Patents
Tube containerInfo
- Publication number
- JPH01139347A JPH01139347A JP29774187A JP29774187A JPH01139347A JP H01139347 A JPH01139347 A JP H01139347A JP 29774187 A JP29774187 A JP 29774187A JP 29774187 A JP29774187 A JP 29774187A JP H01139347 A JPH01139347 A JP H01139347A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- density polyethylene
- olefin resin
- resin
- tube container
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 34
- 229920005989 resin Polymers 0.000 claims abstract description 26
- 239000011347 resin Substances 0.000 claims abstract description 26
- 229920000092 linear low density polyethylene Polymers 0.000 claims abstract description 22
- 239000004707 linear low-density polyethylene Substances 0.000 claims abstract description 22
- 229920001684 low density polyethylene Polymers 0.000 claims abstract description 20
- 239000004702 low-density polyethylene Substances 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 230000004888 barrier function Effects 0.000 claims description 17
- 229920000573 polyethylene Polymers 0.000 claims description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 9
- 229920000642 polymer Polymers 0.000 abstract description 5
- 238000004321 preservation Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 70
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 239000004677 Nylon Substances 0.000 description 10
- 229920001778 nylon Polymers 0.000 description 10
- 239000005977 Ethylene Substances 0.000 description 8
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 8
- 239000012790 adhesive layer Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 229920001903 high density polyethylene Polymers 0.000 description 7
- 239000004700 high-density polyethylene Substances 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 7
- -1 polyethylene Polymers 0.000 description 7
- 239000005038 ethylene vinyl acetate Substances 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-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
- KNDQHSIWLOJIGP-UHFFFAOYSA-N 826-62-0 Chemical compound C1C2C3C(=O)OC(=O)C3C1C=C2 KNDQHSIWLOJIGP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 229920012753 Ethylene Ionomers Polymers 0.000 description 1
- 241001293164 Eutrema japonicum Species 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 235000000760 Wasabia japonica Nutrition 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- NIDNOXCRFUCAKQ-UHFFFAOYSA-N bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2C(O)=O NIDNOXCRFUCAKQ-UHFFFAOYSA-N 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 235000019219 chocolate Nutrition 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
- 239000002537 cosmetic Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 235000015094 jam Nutrition 0.000 description 1
- 235000008960 ketchup Nutrition 0.000 description 1
- 239000002650 laminated plastic Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000010746 mayonnaise Nutrition 0.000 description 1
- 239000008268 mayonnaise Substances 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 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
- 239000011342 resin composition Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- 229940034610 toothpaste Drugs 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
Landscapes
- Tubes (AREA)
- Laminated Bodies (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、粘稠物の包装に用いる絞り出しチューブ容器
に関するもので、より詳細にはエアバック防止性に顕著
に優れた多層プラスチック製絞り出しチューブ容器に関
する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a squeeze tube container used for packaging viscous materials, and more specifically to a squeeze tube container made of multilayer plastic that has outstanding airbag prevention properties. Regarding containers.
（従来の技術）
従来、絞り出し容器、例えば、練歯磨、化粧料或いは食
品類等の高粘度液性物品を収容するための押出しチュー
ブや、ケチャツプ、マヨネーズ、ジャム、チョコレート
等の粘性食品等を収容するための絞り出しくスクイズ）
ボトルとしては、種々の可撓性積層体から成るものが知
られている。(Prior Art) Conventionally, squeeze containers have been used, for example, extruded tubes for storing highly viscous liquid products such as toothpaste, cosmetics, or foods, and viscous foods such as ketchup, mayonnaise, jam, and chocolate. Squeeze to squeeze out)
Bottles made of various flexible laminates are known.
このようなプラスチック可撓性積層体は、一般に、エチ
レン−酢酸ビニル共重合体ケン化物、ナイロン等から成
る酸素バリヤー性層を中間層とし、この両側にポリエチ
レン等のオレフィン樹脂層を積層したものから成ってい
る。デユープの成形に際して、これらの可撓性積層シー
トを重ね合せ接合することにより筒状に成形し、この筒
状胴部の一端部に、樹脂の射出成形により形成されたネ
ジ付押出口とこれに連なる円錐状肩部とから成るものを
接着させ、筒状胴部の他端部を融着等により閉し合わす
。また絞り出しボトルの成形に際して、前述した積層構
造物から成る多層パリソンを割型内で中空成形してボト
ルの形態とする。Such plastic flexible laminates generally consist of an oxygen barrier layer made of saponified ethylene-vinyl acetate copolymer, nylon, etc. as an intermediate layer, and olefin resin layers such as polyethylene layered on both sides. It has become. When forming the duplex, these flexible laminated sheets are overlapped and bonded to form a cylindrical shape, and one end of this cylindrical body is provided with a threaded extrusion port formed by injection molding of resin. Consisting of continuous conical shoulders are glued together, and the other end of the cylindrical body is closed by fusion or the like. Further, when forming a squeeze bottle, the multilayer parison made of the above-mentioned laminated structure is hollow-molded in a split mold to form a bottle.
この多層プラスチック製の絞り出しチューブ容器は、一
定の押圧変形を与え、次いでこれを解除したとき元の容
器形状に復帰する等、復元性が過度に犬であり、このた
めに使用後、蓋で密封し再保存する際、容器内に大量の
空気が吸入され、その結果内容物が容器内酸素により劣
化するという欠点、即ちエアバックを生じる。This squeeze tube container made of multi-layer plastic has excessively poor recovery properties, such as giving a certain pressure deformation and then returning to the original container shape when released, and for this reason, it is sealed with a lid after use. During restorage, a large amount of air is drawn into the container, resulting in the contents being degraded by the oxygen in the container, creating an air bag.
このエアバックを防止するために、特公昭５７−３３２
２３号公報には、チューブ容器を、エチレン−ビニルア
ルコール共重合体及びポリアミドから成る群より選択さ
れた少なくとも１種の酸素バリヤー性樹脂を主体とする
少なくとも１個の層と、弾性率か７００乃至９０００８
ｇ７ｃｍ２の範囲にあるオレフィン系樹脂を主体とする
少なくとも１個の層との間に、前記酸素バリヤー性樹脂
の弾性率ＥＢ以下で且つ前記オレフィン系樹脂の弾性率
Ｅｏ以上の弾性率ＥＡを有する変性オレフィン樹脂を含
有して成る接着介在層を設けた積層構造物で形成し、オ
レフィン系樹脂を主体とする層は、前記酸素バリヤー性
と接着介在層との総和よりも厚い厚みを有し且つオレフ
ィン系樹脂を主体とする層は、その弾性率Ｅ。、８ｇ７
ｃｍ２と厚みｔｏ、 ｃｍの積が９乃至１７０ Ｋｇ／
ｃｍの範囲にあるようにすることが記載されている。In order to prevent this air bag,
No. 23 discloses that the tube container includes at least one layer mainly composed of at least one oxygen barrier resin selected from the group consisting of ethylene-vinyl alcohol copolymer and polyamide, and a layer having an elastic modulus of 700 to 700. 90008
A modified layer having an elastic modulus EA lower than or equal to the elastic modulus EB of the oxygen barrier resin and higher than or equal to the elastic modulus Eo of the olefin resin between the layer and at least one layer mainly composed of an olefin resin in the range of g7 cm2. It is formed of a laminated structure provided with an adhesive intervening layer containing an olefin resin, and the layer mainly composed of an olefin resin has a thickness greater than the sum of the oxygen barrier property and the adhesive intervening layer, and has an olefin resin. The layer mainly composed of resin has an elastic modulus E. ,8g7
The product of cm2 and thickness to, cm is 9 to 170 Kg/
It is described that it should be within the range of cm.
（発明が解決しようとする問題点）
前記従来技術に示されたエアバック防止絞り出しチュー
ブ容器は、類似の多層プラスチック製デユープ容器に比
してエアバック防止性能においてかなり改善されてはい
るが、末だ押圧変形後の復元時間がアルミ箔−プラスチ
ックラミネート型のものに比して短かく、エアバックの
完全防止という目的には不満足、なものである。(Problems to be Solved by the Invention) Although the airbag-preventing squeeze tube containers shown in the prior art are considerably improved in airbag-preventing performance compared to similar multilayer plastic duplex containers, The recovery time after deformation by pressing is shorter than that of the aluminum foil-plastic laminate type, which is unsatisfactory for the purpose of completely preventing airbags.
従って、本発明の目的は、内容物の絞り出し特性に適し
た変形性を有しながら、押圧変形後の復元時間が延長さ
れ、その結果としてエアバック防止性に優れている多層
プラスチック製絞り出しデユープ容器を提供するにある
。Therefore, an object of the present invention is to provide a squeeze-out duplex container made of multilayer plastic that has deformability suitable for the squeezing characteristics of the contents, extends the recovery time after pressure deformation, and has excellent airbag prevention properties as a result. is to provide.
本発明の他の目的は、上記特性に加えて、使用前或いは
使用中の外観特性に優れており、しかも内容物の保存性
や保香性にも優れている絞り出しチューブ容器を提供す
るにある。Another object of the present invention is to provide a squeeze tube container that, in addition to the above characteristics, has excellent appearance characteristics before and during use, and also has excellent preservability and aroma retention of the contents. .
（問題点を解決するための手段）
少なくとも胴部がオレフィン樹脂内層、ガスバリヤ−性
樹脂中間層及びオレフィン樹脂外層の共押出積層体で形
成された絞り出しチューブ容器において、
前記オレフィン樹脂内外層の少なくとも外層がリニア低
密度ポリエチレンと他のエチレン系重合体とを８０：２
０乃至３’Ｏニア０の重量比で含有する組成物から成る
ことを特徴とする絞り出しチューブ容器が提供される。(Means for Solving the Problem) In a squeeze tube container in which at least the body is formed of a coextruded laminate of an olefin resin inner layer, a gas barrier resin intermediate layer, and an olefin resin outer layer, at least the outer layer of the inner and outer olefin resin layers is provided. is 80:2 of linear low density polyethylene and other ethylene polymers.
A squeeze tube container is provided comprising a composition containing a composition in a weight ratio of 0 to 3'O.
（作 用）
本発明の絞り出しチューブ容器は、オレフィン樹脂内層
、ガスバリヤ−性樹脂中間層及びオレフィン樹脂外層の
共押出積層体で少なくともその胴部が形成されるが、上
記オレフィン樹脂内外層の内掛なくとも外層、好適には
内外両層がリニア低密度ポリエチレン（Ｌ−ＬＤＰＥ）
と、通常の低密度ポリエチレン、即ち、高圧法低密度ポ
リエチレン（ＨＰ−ＬＤＰＥ）のような他のエチレン系
重合体とを、８０ ： ２０乃至３’Ｏ： ７０、特に
７０：３０乃至３５・６５の重量比で含有する組成物で
構成されることが顕著な特徴である。即ち、本発明は、
上記多層チューブ容器の少なくとも外層、好適には内外
両層をＬ−’ＬＤＰＥとＨＰ−ＬＤＰＥのような他のエ
チレン系重合体とのブレンド物で構成すると、抑圧変形
後における元の形状への復元時間を著しく延長すること
ができ、これによりエアバック現象を有効に防止し得る
という知見に基づくものである。(Function) The squeezed tube container of the present invention has at least its body formed of a coextruded laminate of an olefin resin inner layer, a gas barrier resin intermediate layer, and an olefin resin outer layer. At least the outer layer, preferably both the inner and outer layers, are linear low density polyethylene (L-LDPE).
and other ethylene-based polymers such as ordinary low-density polyethylene, i.e., high-pressure low-density polyethylene (HP-LDPE), in a ratio of 80:20 to 3'O:70, especially 70:30 to 35.65. A notable feature is that the composition is composed of a composition containing a weight ratio of . That is, the present invention
When at least the outer layer, preferably both the inner and outer layers, of the multilayer tube container are composed of a blend of L-'LDPE and other ethylene polymers such as HP-LDPE, it is possible to restore the original shape after suppressed deformation. This is based on the knowledge that the time can be significantly extended, thereby effectively preventing the airbag phenomenon.
従来、多層プラスチック製絞り出し容器のオレフィン樹
脂内外層としては、弾性率の小さいオレフィン樹脂が適
していると考えられており、このような見地から、高圧
法低密度ポリエチレン（ＨＰ−ＬＤＰＥ）やエチレン−
酢酸ビニル共重合体（ＥＶＡ）が使用されてきた。しか
しながら、ＨＰ−ＬＤＰＥ（ｌ！１ＩＥＶＡは確かに小
すイ弾性率ヲ有するが、それらが有する形状復元性（ク
ッション性）の性質により未た比較的短かい時間の内に
元の形状に復元するという欠点を免れなかった。Conventionally, it has been thought that olefin resins with a low elastic modulus are suitable for the inner and outer olefin resin layers of multilayer plastic squeeze containers, and from this perspective, high-pressure low-density polyethylene (HP-LDPE) and ethylene-
Vinyl acetate copolymer (EVA) has been used. However, although HP-LDPE (1!1IEVA) does have a small elastic modulus, it still recovers to its original shape within a relatively short period of time due to its shape recovery (cushioning) properties. I couldn't escape this drawback.
これに対して、本発明に従い、Ｌ−ＬＤＰＥとＨＰ−Ｌ
ＤＰＥのような他のエチレン系重合体ととを特定のブレ
ンド比でブレンドした組成物をオレフィン樹脂層として
使用すると、エアハック発生時間２乃至５倍に延長化さ
れることが見出されたのである。In contrast, according to the present invention, L-LDPE and HP-L
It was discovered that when a composition prepared by blending DPE with other ethylene polymers at a specific blend ratio was used as the olefin resin layer, the air hack occurrence time was extended by 2 to 5 times. .
本発明において、Ｌ −Ｌ Ｄ Ｐ Ｅと他のエチレン
系重合体とのブレンド物を用いることにより、押圧変形
後の復元時間、即ちエアパック発生時間が著しく延長化
されるという事実は、実験結果として見出されたもので
あり、その理由は未た解明されるに至っていない。しか
しながら、本発明者はその理由を次のように推定してい
る。In the present invention, the fact that the recovery time after pressure deformation, that is, the air pack generation time is significantly prolonged by using a blend of L-LDPE and other ethylene polymers, is based on experimental results. The reason for this has not yet been elucidated. However, the present inventor estimates the reason as follows.
リニア低密度ポリエチレンは、従来普通に使用されてい
る高圧法低密度ポリエチレンや低圧法高密度ポリエチレ
ン（ＨＤＰＥ）には認められない幾つかの特徴を有して
いる。Linear low-density polyethylene has several characteristics not found in conventional high-pressure low-density polyethylene and low-pressure high-density polyethylene (HDPE).
即ち、高圧法低密度ポリエチレンは長鎖分岐を有する分
子構造で、エチレンの単一重合体であるのに対して、リ
ニア低密度ポリエチレンは実質上直鎖状の分子構造を有
し、しかるエチレンと炭素数４乃至８のα−オレフィン
との共重合体から成る。一方低圧法高密度ポリエチレン
は密度（２５℃）が０．９４０乃至０．９６５ｇ／ｃｍ
３の範囲にあり、その分子構造は短かい分岐鎖も殆んど
有していないのに対して、リニア低密度ポリエチレンは
、密度が０９１５乃至０．９３５ｇ／ｃｍ３の範囲にあ
り、前述したα−オレフィンに由来する短鎖分岐鎖を有
する点て相違している。That is, high-pressure low-density polyethylene has a molecular structure with long chain branches and is a single polymer of ethylene, whereas linear low-density polyethylene has a substantially straight-chain molecular structure and consists of ethylene and carbon. It consists of a copolymer with 4 to 8 α-olefins. On the other hand, low pressure high density polyethylene has a density (25°C) of 0.940 to 0.965 g/cm.
3, and its molecular structure has almost no short branched chains, whereas linear low-density polyethylene has a density in the range of 0.915 to 0.935 g/cm3, and its molecular structure has almost no short branched chains. - They differ in that they have short chain branches derived from olefins.
このリニア低密度ポリエチレン（Ｌ−ＬＤＰＥ）は、上
述した化学構造にも関連して他のオレフィン樹脂、例え
は高圧法低密度ポリエチレン（Ｈｐ−ＬＤＰＥ）、高密
度ポリエチレン（ＨＤＰＥ）等に比し、次の第１表に示
すような物性上の相違を有する。This linear low-density polyethylene (L-LDPE) is related to the chemical structure mentioned above, and compared to other olefin resins, such as high-pressure low-density polyethylene (Hp-LDPE) and high-density polyethylene (HDPE), They have differences in physical properties as shown in Table 1 below.
第 １ 表
樹 脂 伸び（＊） 強度（Ｋｇ／ｃｍ） 融点
（１）Ｉ、−ＬＤＰＥ ８５０
３００ １０６〜１２２ＨＰ−ＬＤＰＥ
６００ １２０
９４〜１１４ＨＤＰＥ ８００
２３０ １＋８〜１３３リニア低密
度ポリエヂレンは、上記第１表の通り、他のポリエチレ
ンに比して、大きな伸び、強度及び強靭性（伸びと強度
との積）を有するという特性を有するのに加えて、膜状
物の形で変形させた場合、折れ曲り変形を生じ易いとい
う特性を有している。Table 1 Resin Elongation (*) Strength (Kg/cm) Melting point (1) I, -LDPE 850
300 106~122HP-LDPE
600 120
94~114HDPE 800
As shown in Table 1 above, 230 1+8 to 133 linear low density polyethylene has the characteristics of greater elongation, strength and toughness (product of elongation and strength) compared to other polyethylenes. , when deformed in the form of a film-like material, it has the property of being easily bent and deformed.
かくして、絞り出し容器の表面層中にリニア低］度ポリ
エチレンを含有させると、抑圧変形させたとき、容器壁
に折り曲り変形が生じ易い、この折り曲り変形はその復
元に長時間を要することから、エアパック発生時間が延
長化されるものと推定される。Thus, when linear low-grade polyethylene is contained in the surface layer of a squeezing container, bending deformation is likely to occur in the container wall when suppressed deformation is performed, and this bending deformation takes a long time to restore. It is estimated that the air pack generation time will be extended.
本発明に用いる絞り出し容器における表面層は、リニア
低密度ポリエチレンと他のエチレン系重合体とを前述し
た量比で含有することも重要である。即ちＬ−ＬＤＰＥ
の量が上記範囲よりも少ないと、押圧変形後の復元時間
が本発明の場合に比してかなり短かくなり、エアパック
防止性が十分てなくなる傾向があり、一方Ｌ−ＬＤＰＥ
の量か上記範囲よりも多くなると、共押出積層体の表面
に肌荒れを生じて、外観特性や透明性か不良となる傾向
があり、更に抑圧変形を加えたときに、折れ曲り部に白
筋を発生して、外観特性不良や、ガスバリヤ−性や保香
性の低下を来しやすい。It is also important that the surface layer of the squeezing container used in the present invention contains linear low density polyethylene and other ethylene polymers in the above-mentioned ratio. That is, L-LDPE
If the amount of
If the amount exceeds the above range, the surface of the coextruded laminate tends to become rough, resulting in poor appearance and transparency.Furthermore, when suppressive deformation is applied, white streaks may appear at the bends. This tends to cause poor appearance characteristics and deterioration of gas barrier properties and fragrance retention properties.
（発明の好適態様）
チューブ容器
本発明のデユープ容器の一具体例を示す第１゜２及び３
図において、このチューブ容器は、チューブ本体１と蓋
２とから成っており、デユープ本体１は、後に詳述する
多層パリソンの中空成形により一体に形成されたネジ付
押出口３、これに連なる可撓性の円錐状肩部４及び筒状
の胴部５を有している。(Preferred Embodiment of the Invention) Tube Container Nos. 1, 2 and 3 showing a specific example of the duplex container of the present invention
In the figure, this tube container consists of a tube body 1 and a lid 2, and the duplex body 1 has a threaded extrusion opening 3 integrally formed by hollow molding a multilayer parison, which will be described in detail later, and a screw opening 3 connected thereto. It has a flexible conical shoulder 4 and a cylindrical body 5.
これら各部分を構成する多層パリソンの壁断面を拡大し
て示す第３図において、胴壁５は、酸素バリヤー性熱可
塑性樹脂層６、オレフィン系樹脂層７ａ、７ｂ及びこれ
ら両層の間に介在させた接着介在層８から構成されてい
る。In FIG. 3, which shows an enlarged cross-section of the wall of the multilayer parison constituting each of these parts, the body wall 5 includes an oxygen barrier thermoplastic resin layer 6, olefin resin layers 7a and 7b, and an intervening layer between these layers. It is composed of an adhesive intervening layer 8.
第１及び２図において、この筒状胴部５は、切断された
端縁部９を有し、この端縁部９において、胴部の対面す
る内面層１０．１０が重ね合わせ融着されて、底部を形
成している。In FIGS. 1 and 2, this cylindrical body 5 has a cut edge 9 at which the facing inner layers 10, 10 of the body are overlapped and fused. , forming the bottom.
各樹脂層
本発明において、少なくとも外層、好適には内外両層の
オレフィン系樹脂は、前述したリニア低密度ポリエチレ
ンと他のエチレン系重合体のブレンド物から構成される
。Each resin layer In the present invention, the olefin resin of at least the outer layer, preferably both the inner and outer layers, is composed of a blend of the aforementioned linear low density polyethylene and another ethylene polymer.
このリニア低密度ポリエチレンにおける共単量体として
は、ブテン−１、ペンテン−１，４−メチルペンテン−
１、ヘキセン−１，２−メチル−ブテン−１、オクテン
−１等の炭素数４乃至８のα−オレフィンを挙げること
ができ、これらのα−オレフィンは全体当り１乃至２０
重量％、特に３乃至１５重量％の量で重合体鎖中に組込
まれている。Comonomers in this linear low density polyethylene include butene-1, pentene-1,4-methylpentene-
1, hexene-1,2-methyl-butene-1, octene-1, and other α-olefins having 4 to 8 carbon atoms;
It is incorporated into the polymer chain in an amount of 3% to 15% by weight, in particular 3% to 15% by weight.
他のエチレン系重合体としては、高圧法低密度ポリエチ
レン（ＬＤＰＥ）が有利に使用されるが、他にエチレン
−酢酸ビニル共重合体、特に酢酸ビニル含有量が０．５
乃至２０重量％の共重合体、エチレン−アクリル酸エス
テル共重合体、エチレン−プロピレン共重合体、イオン
架橋エチレン共重合体（アイオノマー）等を用いること
もできる。As other ethylene polymers, high-pressure low density polyethylene (LDPE) is advantageously used, but ethylene-vinyl acetate copolymers, especially those with a vinyl acetate content of 0.5
20% by weight of copolymers, ethylene-acrylic acid ester copolymers, ethylene-propylene copolymers, ionically crosslinked ethylene copolymers (ionomers), etc. can also be used.
酸素バリヤー性樹脂層としては最も好適な例として、エ
チレン−ビニルアルコール共重合体、特にビニルアルコ
ール単体の含有量が４０乃至８５モル％、特に５０乃至
８０モル％のものを挙げることができる。このようなエ
チレン−ビニルアルコール共重合体は、エチレン或いは
エチレンの大部分とプロピレン等の他のオレフィンの少
量成分の組合せと、ギ酸ビニル、酢酸ビニル、プロピオ
ン酸ビニルなど低級脂肪酸のビニルエステルとの共重合
体、特にエチレン−酢酸ビニル共重合体を、ケン化度が
９６％以上、特に９９％以上とな１す
るようにケン化することにより得られる。The most suitable example of the oxygen barrier resin layer is an ethylene-vinyl alcohol copolymer, especially one containing 40 to 85 mol%, especially 50 to 80 mol% of vinyl alcohol alone. Such ethylene-vinyl alcohol copolymers consist of a combination of ethylene or a large portion of ethylene with minor components of other olefins such as propylene, and vinyl esters of lower fatty acids such as vinyl formate, vinyl acetate, and vinyl propionate. It is obtained by saponifying a polymer, particularly an ethylene-vinyl acetate copolymer, to a degree of saponification of 96% or more, particularly 99% or more.
酸素バリヤー性樹脂の他の例としては、ナイロン樹脂、
特にナイロン６、ナイロン８、ナイロン１１、ナイロン
１２、ナイロン６．６、ナイロン６．１０、ナイロン１
０．６、或いはナイロン６−６．６共重合体等を挙げる
ことができる。Other examples of oxygen barrier resins include nylon resin,
Especially nylon 6, nylon 8, nylon 11, nylon 12, nylon 6.6, nylon 6.10, nylon 1
0.6 or nylon 6-6.6 copolymer.
酸素バリヤー性樹脂は、所謂ブレンド物の形で使用する
ことができ、例えば、エチレン−ビニルアルコール共重
合体とナイロン樹脂とのブレンド物を使用することがで
き、更にエチレン−ビニルアルコール共重合体及び／又
はナイロンを主体とし他の樹脂、例えばポリエチレンや
、エチレン−酢酸ビニル共重合体、或いはアイオノマー
の少量を含むブレンド物も、酸素透過係数が５．５×１
０−１２’ｃｃ榔ｃｍ／ｃｍ２・ｓｅｃ−ｃｍＨｇ （
３７℃、０％ＲＨ）以下、特に４．５ ｘ １０−０−
１２ｃｃ−７ｃｍ２・ｓｅｃ・ｃｍＨｇ以下の範囲内に
あれば、本発明の目的に使用し得る。The oxygen barrier resin can be used in the form of a so-called blend. For example, a blend of an ethylene-vinyl alcohol copolymer and a nylon resin can be used, and a blend of an ethylene-vinyl alcohol copolymer and a nylon resin can also be used. / or blends mainly composed of nylon and containing small amounts of other resins, such as polyethylene, ethylene-vinyl acetate copolymers, or ionomers, have an oxygen permeability coefficient of 5.5 x 1.
0-12'cc cm/cm2・sec-cmHg (
37°C, 0% RH) or less, especially 4.5 x 10-0-
If it is within the range of 12cc-7cm2·sec·cmHg or less, it can be used for the purpose of the present invention.
オレフィン樹脂内外層とガスバリヤ−性樹脂中間層とは
、一般に酸変性オレフィン樹脂層を接着剤層として介在
させて接着積層する。酸変性オレフィン樹脂としては、
前述した高密度ポリエチレン、低密度ポリエチレン、中
密度ポリエチレン、リニア低密度ポリエチレン、エチレ
ン−酢酸ビニル共重合体を、
Ａ エチレン系不飽和カルボン酸ニ
アクリル酸、メタクリル酸、マレイン酸、フマル酸、ク
ロトン酸、イタコン酸、シトラコン酸、５−ノルボルネ
ン−２，３−ジカルボン酸、
Ｂ エチレン系不飽和無水カルボン酸：無水マレイン酸
、無水シトラコン酸、５−ノルボルネン−２，３−ジカ
ルボン酸無水物、テトラヒドロ無水フタル酸、
等でグラフト変性したものが使用され、酸乃至酸無水物
によるカルボニル基が１乃至６００ミリモル／１００ｇ
樹脂、特に１０乃至４００ミリモルフ１００ｇ樹脂の濃
度で含有されるものが特に好適に使用される。The inner and outer olefin resin layers and the gas barrier resin intermediate layer are generally adhesively laminated with an acid-modified olefin resin layer interposed as an adhesive layer. As acid-modified olefin resin,
The aforementioned high-density polyethylene, low-density polyethylene, medium-density polyethylene, linear low-density polyethylene, ethylene-vinyl acetate copolymer, A. ethylenically unsaturated carboxylic acid, acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, Itaconic acid, citraconic acid, 5-norbornene-2,3-dicarboxylic acid, B ethylenically unsaturated carboxylic anhydride: maleic anhydride, citraconic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, tetrahydrophthalanhydride A graft modified with acid, etc. is used, and the carbonyl group by acid or acid anhydride is 1 to 600 mmol/100g.
Resins, especially those containing 10 to 400 millimorphs in a concentration of 100 g resin, are particularly preferably used.
層構成
本発明のチューブ容器において、最終容器壁の肉厚は０
，１７乃至１ 、０ｍｍ、特に０３乃至０．７ｍｍの範
囲にあることが望ましい。またオレフィン樹脂内外層の
厚み（ＴＡ）とガスバリヤー性中間層の厚み（Ｔ、）と
は、
ＴＡ： Ｔ、＝ ２ ： １〜２０１
特に ５１〜１５１
の厚み比にあることが望ましく、接着剤層の厚み（Ｔｃ
）は、
ＴＢ：Ｔｃ＝５：１〜１・５
特に ２１〜１２
の厚み比を満足するものであることが望ましい。Layer Structure In the tube container of the present invention, the wall thickness of the final container wall is 0.
,17 to 1,0 mm, particularly preferably in the range of 03 to 0.7 mm. In addition, it is desirable that the thickness of the inner and outer olefin resin layers (TA) and the thickness of the gas barrier intermediate layer (T, ) be in a thickness ratio of TA: T, = 2: 1 to 201, especially 51 to 151. Layer thickness (Tc
) preferably satisfies a thickness ratio of TB:Tc=5:1 to 1.5, particularly 21 to 12.
また、オレフィン樹脂内外層と接着剤との間には、チュ
ーブ状容器の製造の際に副生ずるスクラップ（パリ）樹
脂組成物を介在させることもてきる。Furthermore, a scrap resin composition produced as a by-product during the manufacture of the tubular container may be interposed between the inner and outer olefin resin layers and the adhesive.
本発明のチューブ容器では、容器の全体が前述した共押
出し多層積層体で形成されていることが好適であるが、
胴部のみが共押出積層体で形成され、肩部及び絞り出し
口部が他の樹脂で形成さねでいてもよい。In the tube container of the present invention, it is preferable that the entire container is formed of the above-mentioned coextruded multilayer laminate;
Only the body portion may be formed of a coextruded laminate, and the shoulder portion and the squeezing mouth portion may be formed of other resin.
（発明の効果）
本発明によれば、多層プラスチック製チューブ容器のオ
レフィン樹脂表面層を、リニア低密度ポリエチレンと他
のエチレン系樹脂とのブレンド物で形成することにより
内容物の絞り出しに適した変形性を保有しながら、押圧
変形後の復元時間を延長化し、その結果としてエアバッ
ク防止性能を顕著に向上させることができた。この容器
は使用前及び使用中の外観特性、内容物保存性及び保香
性にも顕著に優れている。(Effects of the Invention) According to the present invention, the olefin resin surface layer of the multilayer plastic tube container is formed of a blend of linear low-density polyethylene and other ethylene resin, thereby making it suitable for squeezing out the contents. While retaining its properties, the recovery time after pressure deformation was extended, and as a result, airbag prevention performance was significantly improved. This container has outstanding appearance characteristics, content preservation properties, and aroma retention properties before and during use.
（実施例） 本発明を次の実施例で説明する。(Example) The invention is illustrated in the following examples.
実施例 １゜
直径４０ｍｍ、有効長さｓｏｏｍｍのスクリューを内蔵
したガスバリヤー性樹脂層用押出機、直径３５ｍｍ、有
効長さ７００ｍｍのスクリューを内蔵し、かつ二つに分
岐したメルトチャンネルを有するアダプターが設けられ
た接着層用押出機そして直径６５＋ｎｍ、有効長さ７０
０ｍｍのスクリューを内蔵し、かつ二つに分岐したメル
トチャンネルを有するアダプターが設けられた内外層で
あるオレフィン系樹脂層用押出機及び対称五層押出用ダ
イスから構成された多層押出機を用いて、ガスバリヤ−
性樹脂としてエチレン含有量３０モル％のエチレン−ビ
ニルアルコール共重合体（ＥＶＯＨ）を中間層とし、オ
レフィン樹脂としてリニア低密度ポリエチレン（Ｌ−Ｌ
ＤＰＥ）と低密度ポリエチレン（ＬＤＰＥ）とのブレン
ド物を内外層とし、中間層と内外層との間に無水マレイ
ン酸グラフト変性したカルボニル基濃度が５０ミリモル
／１００ｇの高密度ポリエチレン（Ｍ−ＨＤＰＥ）を接
着層として介在させた３ｆｉ！５層の溶融パリソンを形
成し、このパリソンを１０℃に冷却された金型に挟み、
ブロー圧力６ Ｋｇ／ｃｍ２にて中空成形して内部口径
７ｍｍ、内容物１８０ｇ入り多層デユープ容器を得た。Example 1 An extruder for a gas barrier resin layer has a built-in screw with a diameter of 40 mm and an effective length of somm, and an adapter that has a built-in screw with a diameter of 35 mm and an effective length of 700 mm and a melt channel branched into two. Adhesive layer extruder equipped with diameter 65+nm, effective length 70
Using a multilayer extruder consisting of an extruder for olefin resin layers (inner and outer layers) equipped with a built-in screw of 0 mm and an adapter having two branched melt channels, and a die for symmetrical five-layer extrusion. , gas barrier
The middle layer is made of ethylene-vinyl alcohol copolymer (EVOH) with an ethylene content of 30 mol% as a plastic resin, and linear low-density polyethylene (LL-L) is used as an olefin resin.
DPE) and low-density polyethylene (LDPE) as the inner and outer layers, and between the middle layer and the inner and outer layers, high-density polyethylene (M-HDPE) with a carbonyl group concentration of 50 mmol/100 g is graft-modified with maleic anhydride. 3fi! with interposed as an adhesive layer! A five-layer molten parison is formed, and this parison is sandwiched between molds cooled to 10°C.
A multilayer duplex container with an internal diameter of 7 mm and a content of 180 g was obtained by blow molding at a blow pressure of 6 Kg/cm2.
胴部の肉厚は４００μであり、各層の比率は内層：接着
層：中間層：接着層：外層＝１０＋０．５ ：２
：０．５ ＋１０ であフた。その結果は第２表の
とおりである。The wall thickness of the body is 400μ, and the ratio of each layer is inner layer:adhesive layer:middle layer:adhesive layer:outer layer=10+0.5:2
:0.5 +10 was enough. The results are shown in Table 2.
第２表
Ｃ，Ｄ、Ｅ、Ｆ・・・・・・・・・実施例Ａ、Ｂ、Ｇ、
Ｈ・・・・・・・・・比較例＊１・・・・重量比
＊２・・・・チューブ容器に内容物としてねり歯！１８
０ｇを充填した後、内容物を９０ｇ絞り出した時に容器
が元の形状に復元するまでの時間（分）を示す。Table 2 C, D, E, F...Examples A, B, G,
H...Comparative example *1...Weight ratio*2...The contents of the tube container are twisted! 18
It shows the time (minutes) it takes for the container to restore its original shape when 90g of the contents are squeezed out after filling 0g.
実施例２゜
実施例１と同様にして、エチレン含有量３０モル％（７
）ＥＶＯＨを中間層とし、Ｌ−ＬＤＰＥとＬＤＰＥとの
ブレンド物を内外層とし、中間層と内外層との間に無水
マレイン酸グラフト変性したカルボニル基濃度が４０ミ
リモル／１００ｇのリニア低密度ポリエチレン（Ｍ−Ｌ
−ＬＤＰＥ） を介在させた３種５層のチューブ容器を
得た。Example 2゜Similarly to Example 1, the ethylene content was 30 mol% (7
) EVOH as the intermediate layer, a blend of L-LDPE and LDPE as the inner and outer layers, and between the intermediate layer and the inner and outer layers, a linear low-density polyethylene with a carbonyl group concentration of 40 mmol/100 g modified by grafting with maleic anhydride ( M-L
-LDPE) Three types of five-layer tube containers were obtained.
このチューブ容器は、内容量が１２０ｇ入りで、内部口
径が５ｍｍで、胴部の肉厚が３５０μであり、かつ各層
の比率が内層：接着層：中間層：接着層：外層＝１０：
１：２：１：Ｂであった。This tube container has an internal capacity of 120 g, an internal diameter of 5 mm, a body wall thickness of 350 μm, and the ratio of each layer is inner layer: adhesive layer: middle layer: adhesive layer: outer layer = 10:
The ratio was 1:2:1:B.
その結果は第３表のとおりである。The results are shown in Table 3.
第３表
Ｉ、Ｊ、Ｋ ・・・・・・・・・実施例り、Ｍ
・・・・・・・・・比較例＊３・・・ 内外層のオレ
フィン樹脂として酢酸ビニル含有量８モル％のエチレン
−酢酸
ビニル共重合体を使用する。Table 3 I, J, K...... Examples, M
Comparative Example *3 Ethylene-vinyl acetate copolymer with a vinyl acetate content of 8 mol% is used as the olefin resin for the inner and outer layers.
＊４・・・・チューブ容器に内容物としてねりわさびを
１２０ｇ充填した後、内容物を６０ｇ絞り出した時に口
頚部にたまってい
る内容物が容器内部に戻されて貫通孔
ができるまでの時間（秒）を示す。*4...After filling a tube container with 120g of wasabi paste and squeezing out 60g of the content, the time (seconds) until the content accumulated in the mouth and neck is returned to the inside of the container and a through hole is formed. ) is shown.
第１図は本発明のチューブ包装体の外観図、第２図はチ
ュ−ブ包装体の断面図、
第３図は多層パリソン壁断面拡大図である。
１・・・チューブ本体、２・・・蓋、３・・・ネジ付押
出口、４・・・肩部、５・・・胴部、６・・・酸素バリ
ヤー性樹脂層、７ａ、７ｂ・・・耐湿性樹脂層、８・・
・接着剤層、９・・・端縁部、１ｏ・・・内面図。FIG. 1 is an external view of the tube package of the present invention, FIG. 2 is a sectional view of the tube package, and FIG. 3 is an enlarged sectional view of the multilayer parison wall. DESCRIPTION OF SYMBOLS 1... Tube body, 2... Lid, 3... Extrusion port with screw, 4... Shoulder part, 5... Body part, 6... Oxygen barrier resin layer, 7a, 7b.・・Moisture-resistant resin layer, 8・・
- Adhesive layer, 9... Edge portion, 1o... Inner view.
Claims (2)
ヤー性樹脂中間層及びオレフィン樹脂外層の共押出積層
体で形成された絞り出しチューブ容器において、 前記オレフィン樹脂内外層の少なくとも外層がリニア低
密度ポリエチレンと他のエチレン系重合体とを８０：２
０乃至３０：７０の重量比で含有する組成物から成るこ
とを特徴とする絞り出しチューブ容器。(1) In a squeeze tube container in which at least the body is formed of a coextruded laminate of an olefin resin inner layer, a gas barrier resin intermediate layer, and an olefin resin outer layer, at least the outer layer of the inner and outer olefin resin layers is made of linear low-density polyethylene, etc. 80:2 with ethylene polymer
A squeeze tube container comprising a composition containing a composition in a weight ratio of 0 to 30:70.
ンである第１項記載の絞り出しチューブ容器。(2) The squeezed tube container according to item 1, wherein the other ethylene polymer is high-pressure low-density polyethylene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29774187A JPH01139347A (en) | 1987-11-27 | 1987-11-27 | Tube container |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29774187A JPH01139347A (en) | 1987-11-27 | 1987-11-27 | Tube container |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01139347A true JPH01139347A (en) | 1989-05-31 |
Family
ID=17850576
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29774187A Pending JPH01139347A (en) | 1987-11-27 | 1987-11-27 | Tube container |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01139347A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001087596A1 (en) * | 2000-05-12 | 2001-11-22 | Pechiney Emballage Flexible Europe | Squeezable containers for flowable products having improved barrier and mechanical properties |
| US6403231B1 (en) | 2000-05-12 | 2002-06-11 | Pechiney Emballage Flexible Europe | Thermoplastic film structures having improved barrier and mechanical properties |
| US6841211B1 (en) | 2000-05-12 | 2005-01-11 | Pechiney Emballage Flexible Europe | Containers having improved barrier and mechanical properties |
| CN104528136A (en) * | 2014-12-08 | 2015-04-22 | 上海三樱包装材料有限公司 | Hose package with fragrance and forming method thereof |
| JP2018526504A (en) * | 2015-08-31 | 2018-09-13 | ダウ グローバル テクノロジーズ エルエルシー | Resin for use as tie layer in multilayer structure and multilayer structure including the same |
| JP2020152395A (en) * | 2019-03-19 | 2020-09-24 | 凸版印刷株式会社 | Pouch for microwave oven heating cooking |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5733223A (en) * | 1980-08-08 | 1982-02-23 | Toshiba Corp | Bearing bracket made of steel plate |
-
1987
- 1987-11-27 JP JP29774187A patent/JPH01139347A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5733223A (en) * | 1980-08-08 | 1982-02-23 | Toshiba Corp | Bearing bracket made of steel plate |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001087596A1 (en) * | 2000-05-12 | 2001-11-22 | Pechiney Emballage Flexible Europe | Squeezable containers for flowable products having improved barrier and mechanical properties |
| US6403231B1 (en) | 2000-05-12 | 2002-06-11 | Pechiney Emballage Flexible Europe | Thermoplastic film structures having improved barrier and mechanical properties |
| US6447860B1 (en) * | 2000-05-12 | 2002-09-10 | Pechiney Emballage Flexible Europe | Squeezable containers for flowable products having improved barrier and mechanical properties |
| US6841211B1 (en) | 2000-05-12 | 2005-01-11 | Pechiney Emballage Flexible Europe | Containers having improved barrier and mechanical properties |
| CN104528136A (en) * | 2014-12-08 | 2015-04-22 | 上海三樱包装材料有限公司 | Hose package with fragrance and forming method thereof |
| JP2018526504A (en) * | 2015-08-31 | 2018-09-13 | ダウ グローバル テクノロジーズ エルエルシー | Resin for use as tie layer in multilayer structure and multilayer structure including the same |
| US10920115B2 (en) | 2015-08-31 | 2021-02-16 | Dow Global Technologies Llc | Resins for use as tie layer in multilayer structure and multilayer structures comprising the same |
| JP2020152395A (en) * | 2019-03-19 | 2020-09-24 | 凸版印刷株式会社 | Pouch for microwave oven heating cooking |
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