JP2008265881A - Multilayered molded container excellent in oxygen absorbability and oxygen shielding property, sheet for multilayer molding, and method for manufacturing sheet for multilayer molding - Google Patents
Multilayered molded container excellent in oxygen absorbability and oxygen shielding property, sheet for multilayer molding, and method for manufacturing sheet for multilayer molding Download PDFInfo
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- 239000001301 oxygen Substances 0.000 title claims abstract description 171
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 171
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 170
- 238000000465 moulding Methods 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title abstract description 28
- 238000000034 method Methods 0.000 title description 14
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 180
- 239000002250 absorbent Substances 0.000 claims abstract description 73
- 230000002745 absorbent Effects 0.000 claims abstract description 73
- 238000010521 absorption reaction Methods 0.000 claims abstract description 35
- 239000002699 waste material Substances 0.000 claims abstract description 33
- 239000010410 layer Substances 0.000 claims description 425
- 229920005989 resin Polymers 0.000 claims description 37
- 239000011347 resin Substances 0.000 claims description 37
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 25
- 239000006096 absorbing agent Substances 0.000 claims description 14
- -1 polypropylene Polymers 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 11
- 239000004743 Polypropylene Substances 0.000 claims description 9
- 229920001155 polypropylene Polymers 0.000 claims description 9
- 239000012790 adhesive layer Substances 0.000 claims description 7
- 238000010030 laminating Methods 0.000 claims description 7
- 229920005672 polyolefin resin Polymers 0.000 claims description 5
- 239000000463 material Substances 0.000 abstract description 47
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- 230000004888 barrier function Effects 0.000 description 7
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- 230000008719 thickening Effects 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000004840 adhesive resin Substances 0.000 description 2
- 229920006223 adhesive resin Polymers 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000006392 deoxygenation reaction Methods 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000002648 laminated material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
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- 238000011084 recovery Methods 0.000 description 2
- 238000007665 sagging Methods 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- UPZFLZYXYGBAPL-UHFFFAOYSA-N 2-ethyl-2-methyl-1,3-dioxolane Chemical compound CCC1(C)OCCO1 UPZFLZYXYGBAPL-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
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- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
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- 235000014413 iron hydroxide Nutrition 0.000 description 1
- XWHPIFXRKKHEKR-UHFFFAOYSA-N iron silicon Chemical compound [Si].[Fe] XWHPIFXRKKHEKR-UHFFFAOYSA-N 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 description 1
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 description 1
- 239000002991 molded plastic Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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Images
Abstract
Description
本発明は、酸素の吸収性と遮蔽性に優れた多層成形容器及び多層成形用シート並びに多層成形用シートの製造方法に関し、詳しくは、食品や医薬品などの内容物保存性に優れた多層成形プラスチック容器において、酸素吸収剤配合の熱可塑性樹脂からなる中間層を均一に形成せしめた多層成形容器及びその多層成形容器を深絞り成形にて製造するための厚肉の多層シート材料、並びに積層方法に特徴を有する多層成形用シートの製造方法、更には酸素吸収剤の配合されたシートサイドトリム屑とスケルトン屑の有効利用に係るものである。 The present invention relates to a multilayer molded container excellent in oxygen absorption and shielding, a multilayer molding sheet, and a method for producing the multilayer molding sheet, and more specifically, a multilayer molded plastic excellent in the preservation of contents such as foods and pharmaceuticals. A multilayer molded container in which an intermediate layer made of a thermoplastic resin containing an oxygen absorbent is uniformly formed in a container, a thick multilayer sheet material for producing the multilayer molded container by deep drawing, and a lamination method The present invention relates to a method for producing a sheet for multilayer molding having characteristics, and further to effective use of sheet side trim waste and skeleton waste mixed with an oxygen absorbent.
容器は日常生活や産業分野などにおいて欠かせないものであるが、最近では金属やガラスよりも、軽量性や耐衝撃性及び成形性や経済性などの観点からプラスチック容器が汎用され、特に、プラスチック容器は食品や医薬品などの用途において重用され必需品となっている。そして、プラスチック容器においては、優れた物性や簡易かつ安価に製造できるなどの理由により、熱可塑性樹脂のプラスチック容器が最も多用されている。
しかし、従前の金属缶やガラス瓶などに比して、一般にプラスチックは微量のガス透過性を有するので、プラスチック容器の場合には器壁を通しての酸素の透過が無視し得ない量で生じ、酸素が食品や医薬品などの内容品を化学変化せしめて、或いは、容器内において酸素が食品の腐敗をもたらす微生物の発育を促進せしめて、収納品の保存性の点で重要な問題となっている。
Containers are indispensable in daily life and industrial fields, but recently plastic containers are more widely used than metal and glass in terms of lightness, impact resistance, moldability and economy, especially plastics. Containers are heavily used in food and pharmaceutical applications and are a necessity. In plastic containers, thermoplastic containers made of thermoplastic resin are most frequently used because of their excellent physical properties and simple and inexpensive production.
However, compared to conventional metal cans and glass bottles, plastics generally have a very small gas permeability, so in the case of plastic containers, oxygen permeation through the vessel wall occurs in an amount that cannot be ignored. It has become an important problem in terms of the storage stability of stored items by chemically changing contents such as foods and pharmaceuticals or by promoting the growth of microorganisms that cause food spoilage in the container.
この問題を解決する手法として、プラスチック容器の器壁を通しての酸素の透過を防止するために、容器壁を多層構造とし、その少なくとも一層に、エチレン−ビニルアルコール共重合体などの酸素遮蔽性を有する樹脂を用いることが行われ、また、容器内の酸素を除去するために、脱酸素剤を使用して、容器壁中に存在する脱酸素剤により容器内の酸素を吸収せしめて容器内を高度の無酸素状態に保持することなどが行われている。
これらの改良技術の代表的な例としては、酸素透過性を有する樹脂に還元性物質を主剤とする脱酸素剤を配合して成る層と、酸素ガス遮断性を有する層とを積層して、外部からの酸素の遮蔽と内部の酸素の吸収を行う、画期的な多層構造の容器が知られている（特許文献１を参照）。
そして、このようなプラスチック容器は、外部から器壁を通しての酸素透過を防ぎ、容器内部の酸素を吸収脱酸素して内容物の保存性を高める非常に優れた容器であるので、酸素の吸収性と遮蔽性に優れた多層成形容器において、更にその機能を高めるために、器壁の層構造や層を形成する樹脂材料或いは酸素吸収剤などにおいて、多くの改良がなされ続けている。
As a technique for solving this problem, in order to prevent the permeation of oxygen through the wall of the plastic container, the container wall has a multilayer structure, and at least one layer has an oxygen shielding property such as an ethylene-vinyl alcohol copolymer. Resin is used, and in order to remove oxygen in the container, an oxygen scavenger is used to absorb the oxygen in the container by the oxygen scavenger present in the container wall. For example, it is maintained in an oxygen-free state.
As a typical example of these improved technologies, a layer formed by blending a resin having oxygen permeability with an oxygen scavenger containing a reducing substance as a main component and a layer having oxygen gas barrier properties are laminated, An epoch-making multilayered container that shields oxygen from outside and absorbs oxygen inside is known (see Patent Document 1).
Such a plastic container is an excellent container that prevents oxygen permeation from the outside through the vessel wall, absorbs and deoxygenates oxygen inside the container, and improves the shelf life of the contents. In order to further enhance the function of the multilayer molded container having excellent shielding properties, many improvements have been made in the layer structure of the vessel wall, the resin material forming the layer, the oxygen absorbent, and the like.
一方、食品や医薬品などの保存用容器として非常に優れた、酸素の吸収性と遮蔽性に富む多層成形容器において、新たな観点から、多層成形容器を成形するための多層シート材料を製造する際に発生するシートサイドトリム屑やスケルトン屑を有効に再利用して、製造コストを下げる課題や、酸素吸収剤配合の酸素吸収性熱可塑性樹脂層や酸素遮蔽性熱可塑性樹脂層を有する多層シート材料を厚肉にして深絞り多層成形容器を製造する要望などが生じている。 On the other hand, when manufacturing multilayer sheet materials for molding multilayer molded containers from a new perspective, they are excellent as storage containers for foods and pharmaceuticals, and have excellent oxygen absorption and shielding properties. Sheet side trim scraps and skeleton scraps that are effectively reused to reduce manufacturing costs, and a multilayer sheet material that has an oxygen-absorbing thermoplastic resin layer or oxygen-shielding thermoplastic resin layer that contains an oxygen absorbent There has been a demand for manufacturing a deep-drawn multilayer molded container with a thick wall.
多層容器を成形するための多層シート材料の製造時に、酸素吸収剤配合の樹脂層が均一に層形成し難いために、高価な酸素吸収性樹脂層を含むシートサイドトリムロスが多量に発生して多層容器の生産コストを低下できないという、新たな観点からの問題に関しては、今までに具体的で有効な解決手段は開示されていない。
酸素吸収剤配合の酸素吸収性熱可塑性樹脂層や酸素遮蔽性熱可塑性樹脂層を有する多層シート材料を厚肉にして深絞り多層成形容器を製造するための具体的な提案も見出せないが、酸素吸収性熱可塑性樹脂層や酸素遮蔽性熱可塑性樹脂層を有する多層シート材料において、厚みが１００〜２００μｍ程度の多少厚肉の多層シートは既に知られている（特許文献２を参照）。しかしこの技術は、多層シート厚み２００μｍ程度で、深絞り成形に必要な１，０００μｍ（１ｍｍ）程度に満たないし、より厚みを薄くしても酸素吸収剤の粒子が表面に突出しないことを目的とするもので、より厚肉にして深絞り成形を目指すものではなく、厚肉多層シートにおいて酸素吸収性樹脂層の均一形成を図るものでもない。
また、酸素遮蔽性樹脂層を有す厚肉の多層容器に工程再粉砕物を使用する提案も開示されているが（特許文献３を参照）、シートの深絞り成形を目指すものではなく、多層シートにおいて酸素吸収性樹脂層の均一形成や高価なシートサイドトリム屑の再利用を図るものでもない。
When manufacturing a multilayer sheet material for molding a multilayer container, it is difficult to uniformly form a resin layer containing an oxygen absorbent, resulting in a large amount of sheet side trim loss including an expensive oxygen-absorbing resin layer. With respect to the problem from a new point of view that the production cost of the multilayer container cannot be reduced, no concrete and effective solution has been disclosed so far.
Although there is no specific proposal for producing a deep-drawn multilayer molded container by thickening a multilayer sheet material having an oxygen-absorbing thermoplastic resin layer or an oxygen-shielding thermoplastic resin layer containing an oxygen absorbent, In a multilayer sheet material having an absorbent thermoplastic resin layer or an oxygen shielding thermoplastic resin layer, a somewhat thick multilayer sheet having a thickness of about 100 to 200 μm is already known (see Patent Document 2). However, this technique has a multilayer sheet thickness of about 200 μm, is less than about 1,000 μm (1 mm) necessary for deep drawing, and is intended to prevent oxygen absorbent particles from protruding to the surface even if the thickness is reduced. Therefore, it does not aim for deep drawing by making it thicker, and it does not aim for uniform formation of the oxygen-absorbing resin layer in the thick multilayer sheet.
Moreover, although the proposal which uses a process repulverization thing for the thick multilayer container which has an oxygen shielding resin layer is also disclosed (refer patent document 3), it does not aim at the deep drawing molding of a sheet | seat. Neither the uniform formation of the oxygen-absorbing resin layer in the sheet nor the reuse of expensive sheet side trim debris is intended.
本発明は、酸素吸収及び遮蔽による収納内容物保存性を有する多層成形容器における、上述の従来の技術の状況において、新たな観点からの課題として、（１）酸素吸収剤配合の酸素吸収性熱可塑性樹脂層及び酸素遮蔽性熱可塑性樹脂層を有する多層シート材料を厚肉にして深絞り多層成形容器を製造し、（２）多層容器を成形するための多層厚肉シート材料の製造時に、酸素吸収剤配合の樹脂層を均一に層形成して、高価な酸素吸収性樹脂層を含むトリムロスの発生を抑制し、また、（３）酸素吸収剤が配合されたトリム屑やスケルトン屑の再利用を図り、多層容器の生産コストを低減する、ことを目指すものである。 The present invention provides, as a problem from a new viewpoint in the above-described conventional state of the art in the multilayer molded container having the stored contents storability due to oxygen absorption and shielding, A deep drawing multilayer molded container is manufactured by thickening a multilayer sheet material having a plastic resin layer and an oxygen shielding thermoplastic resin layer, and (2) oxygen is produced during the manufacture of the multilayer thick sheet material for forming the multilayer container. Uniform layer formation of absorbent-containing resin layer to suppress the generation of trim loss including expensive oxygen-absorbing resin layer. (3) Reuse of trim and skeleton waste containing oxygen absorbent The aim is to reduce the production cost of multilayer containers.
本発明者は、酸素の吸収性と遮蔽性に優れた多層成形容器において、多層シート材料を厚肉にして深絞り多層成形容器を製造し、その際に、酸素吸収剤配合の樹脂層を均一に層形成して、高価な酸素吸収性樹脂層を含むトリムロスの発生を抑制し、また、酸素吸収剤が配合されたトリム屑やスケルトン屑の再利用を図り、多層容器の生産コストを低減する、という課題の解決を目指して、現在汎用されており重要な多層成形容器のひとつである、熱可塑性樹脂からなる内層及び外層と、内層側に位置する酸素吸収剤配合の熱可塑性樹脂からなる第１の中間層と、外層側に位置する酸素遮蔽性の熱可塑性樹脂からなる第２の中間層とを備えた多層成形容器において、有効な課題解決手段を各材料の選定や各層構成の相関の検討或いは積層成形法や深絞り成形性などの種々の観点から、考察勘案し試行実証を行った。
The present inventor manufactured a deep-drawn multilayer molded container by thickening the multilayer sheet material in a multilayer molded container excellent in oxygen absorption and shielding properties. Layer formation to suppress the generation of trim loss including expensive oxygen-absorbing resin layers, and to reduce the production cost of multi-layer containers by reusing trim and skeleton waste containing oxygen absorbent In order to solve the problem, an inner layer and an outer layer made of a thermoplastic resin, which is one of the important multilayer molded containers that are currently widely used, and a thermoplastic resin containing an oxygen absorbent positioned on the inner layer side. In a multilayer molded container having an
そして、考察実証する過程において、酸素吸収剤配合の酸素吸収性熱可塑性樹脂層及び酸素遮蔽性熱可塑性樹脂層を有する多層シート材料を、深絞り成形して多層容器にするために必要な全体の厚肉（大略１ｍｍ［１，０００μｍ］以上）にするために、通常の手法に沿って、熱可塑性樹脂層及び酸素吸収剤配合の酸素吸収性熱可塑性樹脂層と酸素遮蔽性熱可塑性樹脂層を有する多層シート材料とを、厚肉の厚みを持たせるように共押出しにより同時一体成形を行うと、内層側の酸素吸収剤配合の酸素吸収性熱可塑性樹脂層が乱れ均一な層とならず、その結果シートの両端に大量のサイドトリム（多層シートを積層成形する際に生じ、層状態が不適正なために切断除去される、シートの両端の屑）が生じてしまい（図１における例示を参照）、多量のトリム屑によりコスト上昇が避けられないことを知見し得た。
一方、先ず熱可塑性樹脂層と酸素吸収剤配合の酸素吸収性熱可塑性樹脂層からなる内部層を押出し成形などにより積層成形し、次いで熱可塑性樹脂層と酸素遮蔽性熱可塑性樹脂層からなる外部層を押出し成形などにより積層することによって、厚肉に多層積層成形すると酸素吸収性熱可塑性樹脂層がさほど乱れず、サイドトリムの発生が低減されることが判明した。
And in the process of discussion and demonstration, the multilayer sheet material having an oxygen-absorbing thermoplastic resin layer and an oxygen-shielding thermoplastic resin layer blended with an oxygen absorbent is required for the deep drawing to form a multilayer container. In order to make it thick (approximately 1 mm [1,000 μm] or more), an oxygen-absorbing thermoplastic resin layer and an oxygen-absorbing thermoplastic resin layer containing a thermoplastic resin layer and an oxygen absorbent are formed in accordance with a normal method. When performing simultaneous integral molding by coextrusion so that the multilayer sheet material has a thick thickness, the oxygen-absorbing thermoplastic resin layer containing the oxygen absorbent on the inner layer side is not disordered and becomes a uniform layer, As a result, a large amount of side trim (debris at both ends of the sheet, which is generated when the multilayer sheet is laminated and cut and removed because the layer state is inappropriate) is generated at both ends of the sheet (as illustrated in FIG. 1). reference) Cost increase is obtained by finding that the inevitable by a large amount of trim waste.
On the other hand, first, an inner layer composed of a thermoplastic resin layer and an oxygen-absorbing thermoplastic resin layer containing an oxygen absorbent is laminated by extrusion molding, and then an outer layer composed of a thermoplastic resin layer and an oxygen-shielding thermoplastic resin layer. It has been found that, by laminating by extrusion molding or the like, when the multilayer lamination molding is performed thickly, the oxygen-absorbing thermoplastic resin layer is not significantly disturbed, and the occurrence of side trim is reduced.
驚くべきことに、多層シート材料を押出成形する際に、サイドトリム屑（及びスケルトン屑）を混入した樹脂層を酸素遮蔽性熱可塑性樹脂層の外層側に設けると、酸素吸収性熱可塑性樹脂層がよりいっそう乱れず均一な層となり、サイドトリムの発生が大幅に低減されることも判明した。
この理由は未だ明確ではないが、酸素吸収剤が配合された酸素吸収性樹脂における酸素吸収剤が鉄系材料で他層に比較して重量があり層乱れの原因となるが、サイドトリム屑を混入した樹脂層を酸素遮蔽性熱可塑性樹脂層の外層側に設けると、サイドトリム屑にも多量の鉄系酸素吸収剤が混入されているから、酸素吸収剤が配合された酸素吸収性樹脂層とサイドトリム屑を混入した樹脂層とが層バランスを取りシート成形安定性が増すからではないかと推測される。
そして、本発明においては、サイドトリム屑及びスケルトン屑（厚肉の多層積層シートを多数個取りにて深絞り成形して打ち抜いた後の残余のシート屑）を各層に混入し或いは新たな層として再利用をも図ることをも特徴としている。
Surprisingly, when extruding a multilayer sheet material, if a resin layer mixed with side trim debris (and skeleton debris) is provided on the outer layer side of the oxygen-shielding thermoplastic resin layer, the oxygen-absorbing thermoplastic resin layer It has also been found that a more uniform layer with less disturbance and the occurrence of side trim is greatly reduced.
The reason for this is not clear yet, but the oxygen absorbent in the oxygen absorbent resin containing the oxygen absorbent is an iron-based material that is heavier than the other layers and causes layer disturbance. If the mixed resin layer is provided on the outer layer side of the oxygen-shielding thermoplastic resin layer, a large amount of iron-based oxygen absorbent is also mixed in the side trim scraps, so the oxygen-absorbing resin layer in which the oxygen absorbent is blended And the resin layer mixed with the side trim debris are assumed to balance the layers and increase sheet molding stability.
In the present invention, side trim scraps and skeleton scraps (remaining sheet scraps after deep drawing and punching a large number of thick multilayer laminated sheets) are mixed into each layer or as new layers It is also characterized by reusing.
かくして、本発明は第一の基本発明として、「熱可塑性樹脂からなる第１層及び第２層と、両層の中間に位置する酸素吸収剤配合の熱可塑性樹脂からなる中間層とを備えた内部層、及び、熱可塑性樹脂からなる第３層及び第４層と、両層の中間に位置する酸素遮蔽性の熱可塑性樹脂からなる中間層とを備えた外部層とからなることを特徴とする、酸素の吸収性と遮蔽性に優れた、深絞り成形による多層成形容器。」を構築し、また、第二の基本発明として、「熱可塑性樹脂からなる第１層及び第２層と、両層の中間に位置する酸素吸収剤配合の熱可塑性樹脂からなる中間層とを備えた内部層シートを成形し、次いで、熱可塑性樹脂からなる第３層及び第４層と、両層の中間に位置する酸素遮蔽性の熱可塑性樹脂からなる中間層とを備えた外部層を設けることにより成形した多層成形用シートを深絞り成形したことを特徴とする、酸素の吸収性と遮蔽性に優れた多層成形容器。」を構築するものである。 Thus, as a first basic invention, the present invention includes "a first layer and a second layer made of a thermoplastic resin, and an intermediate layer made of a thermoplastic resin blended with an oxygen absorbent located between the two layers. It is characterized by comprising an outer layer comprising an inner layer, a third layer and a fourth layer made of a thermoplastic resin, and an intermediate layer made of an oxygen-shielding thermoplastic resin located between the two layers. A multi-layer molded container by deep drawing excellent in oxygen absorption and shielding properties, and as a second basic invention, "first and second layers made of thermoplastic resin; Forming an inner layer sheet comprising an intermediate layer made of a thermoplastic resin blended with an oxygen absorbent located between the two layers; then, the third and fourth layers made of a thermoplastic resin; With an intermediate layer made of an oxygen-shielding thermoplastic resin located on the outside Wherein the molded deep drawing multilayer molded sheet molded by providing a absorbent and barrier properties superior multilayer molded container of oxygen. "Is intended to build.
ところで、背景技術における先の特許文献及びその他の特許文献を精査しても、上述の本発明の特異的な構成及び格別の特徴は窺うことができない。
なお、特開２０００−３７８２３号公報においては、保護層−酸素バリア層−基材層−脱酸素層−シーラント（シール）層からなる、酸素吸収性と遮蔽性を備えた五層の積層材料が開示され（その特許請求の範囲の請求項１，３）、層構成が本発明の多層成形用シートと見掛け上近似し、積層材料全体が２５０乃至１５００μ程度の厚肉であることも記載され（その段落００４３）、本発明の厚肉と同程度である。しかし、本発明においては、（ｉ）多層成形シートを深絞りして多層容器を成形するものであり、（ｉｉ）その多層成形シートは、先ず熱可塑性樹脂層と酸素吸収剤配合の酸素吸収性熱可塑性樹脂層からなる内部層を押出し成形などにより積層成形し、次いで熱可塑性樹脂層と酸素遮蔽性熱可塑性樹脂層からなる外部層を押出し成形などにより積層することによって、（ｉｉｉ）厚肉に多層積層成形しても酸素吸収性熱可塑性樹脂層がさほど乱れず、サイドトリムの発生が低減されることを特徴とするが、かかる本発明の特異的な構成の要件（ｉ及びｉｉ）と格別の作用効果（ｉｉｉ）は、上記の公報には記載も示唆もされていず、当公報の記載から本発明を当業者が窺うこともできない。
By the way, even if the previous patent document and other patent documents in the background art are scrutinized, the above-described specific configuration and special features of the present invention cannot be obtained.
In JP-A-2000-37823, a five-layer laminate material having an oxygen-absorbing property and a shielding property composed of a protective layer-oxygen barrier layer-base material layer-deoxygenation layer-sealant (seal) layer is provided. It is disclosed (claims 1 and 3 in the scope of claims), and it is also described that the layer structure is similar in appearance to the multilayer molding sheet of the present invention, and the entire laminated material is about 250 to 1500 μm thick ( The paragraph 0043) is comparable to the thick wall of the present invention. However, in the present invention, (i) a multilayer container is formed by deep-drawing a multilayer molded sheet, and (ii) the multilayer molded sheet is first composed of a thermoplastic resin layer and an oxygen absorbent. (Iii) Thickness is achieved by laminating an inner layer composed of a thermoplastic resin layer by extrusion molding and then laminating an outer layer composed of a thermoplastic resin layer and an oxygen shielding thermoplastic resin layer by extrusion molding, etc. The oxygen-absorbing thermoplastic resin layer is not significantly disturbed even by multilayer lamination molding, and the occurrence of side trim is reduced. However, the requirements (i and ii) of the specific configuration of the present invention are exceptional. The above effect (iii) is neither described nor suggested in the above-mentioned publication, and the person skilled in the art cannot obtain the present invention from the description in this publication.
本発明においては、以上のような認識を基礎として基本発明が構築され、基本発明を展開して更に多種の発明群が形成された。そして、発明の課題を解決する手段を、本発明が創作される経緯及び本発明の基本的な構成と特徴に沿って概述したので、ここでその発明の全体を明確にするために、本発明の全体を俯瞰する。
本発明は、次の発明単位群から構成されるものであって、第一発明及び第二発明更には第九発明と第十発明を基本的発明とし、それら以外の発明は、基本的発明を具体化ないしは実施態様化するものである。
In the present invention, the basic invention was constructed based on the above recognition, and the basic invention was developed to form various invention groups. The means for solving the problems of the present invention have been outlined along with the background of the creation of the present invention and the basic configuration and features of the present invention. In order to clarify the whole of the present invention, the present invention is described here. An overview of the whole.
The present invention is composed of the following invention unit groups, and the first invention, the second invention, the ninth invention and the tenth invention are the basic inventions, and the other inventions are the basic inventions. It is embodied or embodied.
第一発明： 熱可塑性樹脂からなる第１層及び第２層と、両層の中間に位置する酸素吸収剤配合の熱可塑性樹脂からなる中間層とを備えた内部層、及び、熱可塑性樹脂からなる第３層及び第４層と、両層の中間に位置する酸素遮蔽性の熱可塑性樹脂からなる中間層とを備えた外部層とからなることを特徴とする、酸素の吸収性と遮蔽性に優れた、深絞り成形による多層成形容器。
第二発明： 熱可塑性樹脂からなる第１層及び第２層と、両層の中間に位置する酸素吸収剤配合の熱可塑性樹脂からなる中間層とを備えた内部層シートを成形し、次いで、熱可塑性樹脂からなる第３層及び第４層と、両層の中間に位置する酸素遮蔽性の熱可塑性樹脂からなる中間層とを備えた外部層を設けることにより成形した多層成形用シートを深絞り成形したことを特徴とする、酸素の吸収性と遮蔽性に優れた多層成形容器。
第三発明： 厚肉の多層成形用シートの深絞り成形によることを特徴とする、第一発明又は第二発明における酸素の吸収性と遮蔽性に優れた多層成形容器。
第四発明： 酸素遮蔽性の熱可塑性樹脂からなる中間層の両側層に接着剤層が設けられたことを特徴とする、第一発明〜第三発明のいずれかにおける酸素の吸収性と遮蔽性に優れた多層成形容器。
第五発明： 第１層〜第４層の熱可塑性樹脂がポリプロピレン系樹脂であり、酸素遮蔽性の熱可塑性樹脂がエチレン−ビニルアルコール共重合体であり、酸素吸収剤配合の熱可塑性樹脂がポリオレフィン系樹脂であることを特徴とする、第一発明〜第三発明のいずれかにおける酸素の吸収性と遮蔽性に優れた多層成形容器。
第六発明： 酸素吸収剤が鉄系脱酸素剤であることを特徴とする、第一発明〜第五発明のいずれかにおける酸素の吸収性と遮蔽性に優れた多層成形容器。
第七発明： 酸素遮蔽性熱可塑性樹脂からなる中間層の外層側に、廃棄されるシートサイドトリム屑及びスケルトン屑が混入された層をさらに設けたことを特徴とする、第一発明又は第二発明における酸素の吸収性と遮蔽性に優れた多層成形容器。
第八発明： 酸素吸収剤配合の熱可塑性樹脂からなる中間層に、廃棄されるシートサイドトリム屑及びスケルトン屑が混入されたことを特徴とする、第一発明又は第二発明における酸素の吸収性と遮蔽性に優れた多層成形容器。
第九発明： 熱可塑性樹脂からなる第１層及び第２層と、両層の中間に位置する酸素吸収剤配合の熱可塑性樹脂からなる中間層とを備えた内部層、及び、熱可塑性樹脂からなる第３層及び第４層と、両層の中間に位置する酸素遮蔽性の熱可塑性樹脂からなる中間層とを備えた外部層とからなり、酸素遮蔽性熱可塑性樹脂からなる中間層の外層側に、廃棄されるシートサイドトリム屑及びスケルトン屑が混入された層を更に設ける、又は酸素吸収剤配合の熱可塑性樹脂からなる中間層に、廃棄されるシートサイドトリム屑及びスケルトン屑が混入されることを特徴とする、酸素の吸収性と遮蔽性に優れた多層成形用シート。
第十発明： 熱可塑性樹脂からなる第１層及び第２層と、両層の中間に位置する酸素吸収剤配合の熱可塑性樹脂からなる中間層とを備えた内部層シートを成形し、次いで、熱可塑性樹脂からなる第３層及び第４層と、両層の中間に位置する酸素遮蔽性の熱可塑性樹脂からなる中間層とを備えた外部層を積層成形することを特徴とする、酸素の吸収性と遮蔽性に優れた多層成形用シートの製造方法。
1st invention: From the inner layer provided with the 1st layer and 2nd layer which consist of a thermoplastic resin, and the intermediate | middle layer which consists of a thermoplastic resin of the oxygen absorbent mixing located in the middle of both layers, and a thermoplastic resin Absorptive and shielding properties of oxygen, characterized by comprising an outer layer comprising a third layer and a fourth layer, and an intermediate layer made of an oxygen-shielding thermoplastic resin located between the two layers. Excellent multi-layer molded container by deep drawing.
2nd invention: The inner layer sheet | seat provided with the 1st layer and 2nd layer which consist of a thermoplastic resin, and the intermediate | middle layer which consists of a thermoplastic resin of the oxygen absorber mixing | blending located in the middle of both layers, Then, A multilayer molding sheet formed by providing an outer layer comprising a third layer and a fourth layer made of a thermoplastic resin and an intermediate layer made of an oxygen-shielding thermoplastic resin located between the two layers A multilayer molded container excellent in oxygen absorption and shielding, characterized by being drawn.
Third invention: A multilayer molded container excellent in oxygen absorption and shielding properties according to the first or second invention, characterized by deep drawing of a thick multilayer molding sheet.
Fourth invention: Oxygen absorption and shielding properties according to any one of the first to third inventions, characterized in that an adhesive layer is provided on both side layers of the intermediate layer made of an oxygen shielding thermoplastic resin. Excellent multi-layer molded container.
Fifth Invention: The thermoplastic resin of the first to fourth layers is a polypropylene resin, the oxygen shielding thermoplastic resin is an ethylene-vinyl alcohol copolymer, and the thermoplastic resin containing an oxygen absorbent is a polyolefin. A multilayer molded container excellent in oxygen absorptivity and shielding property according to any one of the first to third inventions, characterized in that it is a resin.
6th invention: The multilayer molded container excellent in the absorptivity and shielding property of oxygen in any one of the 1st invention-the 5th invention characterized by an oxygen absorber being an iron-type oxygen absorber.
7th invention: The 1st invention or 2nd characterized by further providing the layer which the waste sheet side trim waste and the skeleton waste were mixed in the outer layer side of the intermediate | middle layer which consists of oxygen shielding thermoplastic resins A multilayer molded container excellent in oxygen absorption and shielding properties in the invention.
Eighth Invention: Oxygen absorbability in the first invention or the second invention, characterized in that discarded sheet side trim waste and skeleton waste are mixed in an intermediate layer made of a thermoplastic resin containing an oxygen absorbent. Multi-layer molded container with excellent shielding properties.
Ninth invention: From an inner layer including a first layer and a second layer made of a thermoplastic resin, and an intermediate layer made of a thermoplastic resin blended with an oxygen absorbent located between the two layers, and the thermoplastic resin And an outer layer comprising an intermediate layer made of an oxygen-shielding thermoplastic resin located between the two layers, and an outer layer of the intermediate layer made of an oxygen-shielding thermoplastic resin Further, a layer mixed with discarded seat side trim scraps and skeleton scraps is provided on the side, or an intermediate layer made of a thermoplastic resin containing oxygen absorbent is mixed with discarded seat side trim scraps and skeleton scraps. A multilayer molding sheet excellent in oxygen absorption and shielding properties.
Tenth invention: Forming an inner layer sheet comprising a first layer and a second layer made of a thermoplastic resin, and an intermediate layer made of a thermoplastic resin blended with an oxygen absorbent located between the two layers, An outer layer comprising a third layer and a fourth layer made of a thermoplastic resin and an intermediate layer made of an oxygen-shielding thermoplastic resin located between the two layers is laminated and formed, A method for producing a multilayer molding sheet having excellent absorbency and shielding properties.
本発明においては、深絞り成形による、酸素の吸収性と遮蔽性に優れた多層成形容器の製造が可能となり、また、多層成形シート材料において、シートサイドトリム率が大幅に減少し、多層成形シート材料の中間層の垂れ下がりも発生せず、それにより厚肉シートであっても、多層シート材料の生産安定性が向上する。
更に、トリム屑とスケルトン屑の層材料としての再利用によって他層の材料の使用量が軽減され、トリム屑とスケルトン屑の再使用による高価な酸素吸収剤の回収使用からのコストダウンへの寄与が大きくなっている。
In the present invention, it becomes possible to produce a multilayer molded container excellent in oxygen absorption and shielding by deep drawing, and in the multilayer molded sheet material, the sheet side trim ratio is greatly reduced. No sagging of the intermediate layer of the material occurs, thereby improving the production stability of the multilayer sheet material even for thick sheets.
Furthermore, the reuse of trim and skeleton waste as a layer material reduces the amount of material used in other layers, and the cost reduction from the recovery and use of expensive oxygen absorbents by the reuse of trim and skeleton waste. Is getting bigger.
本発明については、課題を解決するための手段として、本発明の基本的な構成と特徴を前述したが、以下においては、前述した本発明群の発明（本発明群の発明を「本発明」と略記することがある）の実施の形態を、図面を参照しながら具体的に詳しく説明する。 Regarding the present invention, as a means for solving the problems, the basic configuration and features of the present invention have been described above. In the following, the invention of the present invention group (the invention of the present invention group is referred to as “the present invention”). ) Will be described in detail with reference to the drawings.
１．基本的な構成と特徴
本発明は、基本的に、深絞り成形による、酸素の吸収性と遮蔽性に優れ食品或いは医薬品などの内容物保存性の高い多層成形容器に関し、更に、かかる多層成形プラスチック容器において、酸素吸収剤配合の熱可塑性樹脂からなる中間層を均一に形成せしめた多層成形容器及びその多層成形容器を製造するための多層シート材料、並びにそれらの製造方法に係るものであり、また、シートサイドトリム屑とスケルトン屑の再使用による高価な酸素吸収剤の回収使用からのコストダウンへの寄与を行うものである。
そして、具体的に、（１）酸素吸収剤配合の酸素吸収性熱可塑性樹脂層及び酸素遮蔽性熱可塑性樹脂層を有する多層シート材料を深絞り成形して多層成形容器を製造し、（２）多層容器を成形するための多層厚肉シート材料の製造時に、特定の積層方法（段落００２１に記載）の採用により、酸素吸収剤配合の樹脂層を均一に層形成して、高価な酸素吸収性樹脂層を含むトリムロスの発生を抑制し、（３）更に、トリム屑とスケルトン屑を層中に混合或いは他層として使用して多層容器の生産コストを低減することを特徴とするものである。
1. BACKGROUND OF THE
Specifically, (1) a multilayer sheet material having an oxygen-absorbing thermoplastic resin layer and an oxygen-shielding thermoplastic resin layer blended with an oxygen absorbent is deep-drawn to produce a multilayer molded container; (2) When manufacturing multi-layered thick sheet material for forming multi-layer containers, a specific layering method (described in paragraph 0021) is used to uniformly form a resin layer containing an oxygen absorbent so that expensive oxygen absorption Generation | occurrence | production of the trim loss containing a resin layer is suppressed, (3) Furthermore, trim waste and skeleton waste are mixed in a layer, or it uses as another layer, It is characterized by reducing the production cost of a multilayer container.
２．酸素の吸収性と遮蔽性に優れた、深絞り多層成形容器
段落０００３の背景技術において前述したように、以前から、酸素透過性を有する樹脂に還元性物質を主剤とする脱酸素剤を配合してなる層と、酸素ガス遮断性を有する層とを積層して、外部からの酸素の透過阻止と内部の酸素の吸収を行う、画期的な多層構造容器が知られている。
しかし、酸素吸収剤配合の酸素吸収性熱可塑性樹脂層及び酸素遮蔽性熱可塑性樹脂層を有する多層シート材料を使用して、複雑な形状や構造の容器を成形するには、全体の厚みが大略１ｍｍ（１，０００μｍ）以上の多層シート材料を形成して、深絞り成形する必要があるが、従来では、酸素吸収剤配合の酸素吸収性熱可塑性樹脂層及び酸素遮蔽性熱可塑性樹脂層を有する多層シート材料において、そのような厚肉の材料による深絞り成形は試みられていない。
2. Deep-drawing multilayer molded container with excellent oxygen absorption and shielding properties As previously mentioned in the background art of paragraph 0003, an oxygen-permeable resin has previously been blended with a deoxidizing agent mainly composed of a reducing substance. An epoch-making multilayer structure container is known in which an oxygen layer and an oxygen gas barrier layer are laminated to prevent permeation of oxygen from outside and absorb internal oxygen.
However, when a container having a complicated shape or structure is formed using a multilayer sheet material having an oxygen-absorbing thermoplastic resin layer and an oxygen-shielding thermoplastic resin layer containing an oxygen absorbent, the overall thickness is roughly Although it is necessary to form a multilayer sheet material of 1 mm (1,000 μm) or more and deep-draw molding, conventionally, it has an oxygen-absorbing thermoplastic resin layer and an oxygen-shielding thermoplastic resin layer containing an oxygen absorbent. In the multilayer sheet material, no deep drawing with such a thick material has been attempted.
本発明は、酸素の吸収性と遮蔽性に優れた多層容器において、大略の厚みが、好ましくは１ｍｍ以上の多層容器成形用の厚肉多層シート材料を形成して、それを深絞り成形し多層容器となしたものであって、「熱可塑性樹脂からなる第１層及び第２層と、両層の中間に位置する酸素吸収剤配合の熱可塑性樹脂からなる中間層とを備えた内部層、及び、熱可塑性樹脂からなる第３層及び第４層と、両層の中間に位置する酸素遮蔽性の熱可塑性樹脂からなる中間層とを備えた外部層」の層構成により、１ｍｍ以上の厚みシートの形成がなされ、それを深絞り成形することにより、本発明における基本発明のひとつである、第一発明における、「熱可塑性樹脂からなる第１層及び第２層と、両層の中間に位置する酸素吸収剤配合の熱可塑性樹脂からなる中間層とを備えた内部層、及び、熱可塑性樹脂からなる第３層及び第４層と、両層の中間に位置する酸素遮蔽性の熱可塑性樹脂からなる中間層とを備えた外部層とからなることを特徴とする、酸素の吸収性と遮蔽性に優れた、深絞り成形による多層成形容器」が構築される。
なお、本明細書での深絞り成形とは、容器における高さ／口径の比が０．８以上となる成形をいう。
The present invention provides a multilayer container excellent in oxygen absorption and shielding properties, and is formed by forming a thick multilayer sheet material for molding a multilayer container having an approximate thickness of preferably 1 mm or more, and then deep-drawing it. An inner layer comprising a first layer and a second layer made of a thermoplastic resin, and an intermediate layer made of a thermoplastic resin blended with an oxygen absorbent located between the two layers, And a thickness of 1 mm or more by a layer configuration of an “outer layer comprising a third layer and a fourth layer made of a thermoplastic resin and an intermediate layer made of an oxygen-shielding thermoplastic resin located between the two layers” In the first invention, which is one of the basic inventions in the present invention, a sheet is formed and deep-drawn, and “the first layer and the second layer made of a thermoplastic resin are placed between the two layers. From thermoplastic resin containing oxygen absorber An outer layer comprising an inner layer comprising an intermediate layer, a third layer and a fourth layer comprising a thermoplastic resin, and an intermediate layer comprising an oxygen-shielding thermoplastic resin located between the two layers. A multilayer molded container by deep drawing excellent in oxygen absorption and shielding properties, which is characterized by comprising:
Note that deep drawing in this specification refers to molding in which the ratio of height / bore in the container is 0.8 or more.
ここで、多層成形容器の一例としての、層構成が図２に図示されている。図中の上側が容器の外部で、図中の下側が容器の内部側に相当する。
熱可塑性樹脂からなる第１層〜第４層は、１１と１３と１４と１７であり、内層側に位置する酸素吸収剤配合の熱可塑性樹脂からなる中間層は１２であり、外層側に位置する酸素遮蔽性の熱可塑性樹脂からなる中間層は１６であり、その両側の接着剤層は１５である。
Here, the layer structure as an example of the multilayer molded container is shown in FIG. The upper side in the figure corresponds to the outside of the container, and the lower side in the figure corresponds to the inner side of the container.
The first to fourth layers made of thermoplastic resin are 11, 13, 14, and 17, and the intermediate layer made of a thermoplastic resin blended with an oxygen absorbent located on the inner layer side is 12 and is located on the outer layer side. The intermediate layer made of oxygen-shielding thermoplastic resin is 16, and the adhesive layers on both sides thereof are 15.
ここで、シート材料を厚肉にするために、熱可塑性樹脂からなる第１層及び第２層と、両層の中間に位置する酸素吸収剤配合の熱可塑性樹脂からなる中間層とを備えた内部層に、熱可塑性樹脂からなる第３層及び第４層と、両層の中間に位置する酸素遮蔽性の熱可塑性樹脂からなる中間層とを備えた外部層を組み合わせ積層して、積層構造全体として、好ましくは大略１，０００μｍ以上（１ｍｍ以上）の厚肉に成形する。 Here, in order to thicken the sheet material, the first layer and the second layer made of a thermoplastic resin, and an intermediate layer made of a thermoplastic resin blended with an oxygen absorbent located between the two layers were provided. A laminated structure in which an outer layer including a third layer and a fourth layer made of a thermoplastic resin and an intermediate layer made of an oxygen-shielding thermoplastic resin located between the two layers is laminated on the inner layer. As a whole, it is preferably formed into a thick wall of approximately 1,000 μm or more (1 mm or more).
３．酸素吸収剤配合の熱可塑性樹脂層の均一形成
注目されるべきことに、熱可塑性樹脂からなる第１層及び第２層と、両層の中間に位置する酸素吸収剤配合の熱可塑性樹脂からなる中間層とを備えた内部層を予め設ければ、中間層が層構成において対称的となり、酸素吸収性熱可塑性樹脂層（第１の中間層）のシート中央部の層部分の垂れ下りが抑制され、その結果として酸素吸収剤が熱可塑性樹脂層中に、大略均一に配合され存在することになり、シートの中央部と両端部におけるシートの層構成が大略均一となる。
そして、先ず、熱可塑性樹脂からなる第１層及び第２層と、両層の中間に位置する酸素吸収剤配合の熱可塑性樹脂からなる中間層とを備えた内部層シートを成形し、次いで、熱可塑性樹脂からなる第３層及び第４層と、両層の中間に位置する酸素遮蔽性の熱可塑性樹脂からなる中間層とを備えた外部層を設けることにより、酸素吸収性樹脂層と酸素遮蔽性樹脂層及び他の熱可塑性樹脂層の各層が大略均一に層形成されることになる。
3. Uniform formation of a thermoplastic resin layer containing an oxygen absorbent It should be noted that the first and second layers made of a thermoplastic resin, and a thermoplastic resin containing an oxygen absorbent located between the two layers. If an inner layer including an intermediate layer is provided in advance, the intermediate layer becomes symmetrical in the layer structure, and drooping of the layer portion in the center of the sheet of the oxygen-absorbing thermoplastic resin layer (first intermediate layer) is suppressed. As a result, the oxygen absorbent is present in the thermoplastic resin layer in a substantially uniform manner, so that the sheet layer configuration at the center and both ends of the sheet is substantially uniform.
First, an inner layer sheet comprising a first layer and a second layer made of a thermoplastic resin and an intermediate layer made of a thermoplastic resin blended with an oxygen absorbent located between the two layers is formed, and then By providing an outer layer including the third layer and the fourth layer made of thermoplastic resin and an intermediate layer made of oxygen-shielding thermoplastic resin located between the two layers, the oxygen-absorbing resin layer and oxygen Each layer of the shielding resin layer and the other thermoplastic resin layer is substantially uniformly formed.
しかして、第二発明の「熱可塑性樹脂からなる第１層及び第２層と、両層の中間に位置する酸素吸収剤配合の熱可塑性樹脂からなる中間層とを備えた内部層シートを成形し、次いで、熱可塑性樹脂からなる第３層及び第４層と、両層の中間に位置する酸素遮蔽性の熱可塑性樹脂からなる中間層とを備えた外部層を設けることにより成形した多層成形用シートを深絞り成形したことを特徴とする、酸素の吸収性と遮蔽性に優れた多層成形容器。」、及び第十発明の「熱可塑性樹脂からなる第１層及び第２層と、両層の中間に位置する酸素吸収剤配合の熱可塑性樹脂からなる中間層とを備えた内部層シートを成形し、次いで、熱可塑性樹脂からなる第３層及び第４層と、両層の中間に位置する酸素遮蔽性の熱可塑性樹脂からなる中間層とを備えた外部層を積層成形することを特徴とする、酸素の吸収性と遮蔽性に優れた多層成形用シートの製造方法」の各発明が構築される。 Thus, according to the second invention, “an inner layer sheet provided with a first layer and a second layer made of a thermoplastic resin and an intermediate layer made of a thermoplastic resin blended with an oxygen absorbent located between the two layers is formed. And then forming a third layer and a fourth layer made of a thermoplastic resin and an outer layer comprising an intermediate layer made of an oxygen-shielding thermoplastic resin located between the two layers. A multi-layer molded container excellent in oxygen absorption and shielding properties, characterized by deep drawing of a sheet for use, and “a first layer and a second layer made of a thermoplastic resin” in the tenth invention, Forming an inner layer sheet comprising an intermediate layer made of a thermoplastic resin blended with an oxygen absorbent located in the middle of the layers, and then, between the third and fourth layers made of a thermoplastic resin, And an intermediate layer made of an oxygen-shielding thermoplastic resin. Wherein the laminated molded parts layer, each invention in the absorption of the oxygen and a manufacturing method excellent sheet for multi-layer molded shielding property "is constructed.
ここで、熱可塑性樹脂からなる第１層及び第２層と、両層の中間に位置する酸素吸収剤配合の熱可塑性樹脂からなる中間層とを備えた内部層シートは、押出成形や共押出或いはサンドイッチラミネーションなどの通常の各種ラミネート法（積層法）により成形され、次いで、熱可塑性樹脂からなる第３層及び第４層と、両層の中間に位置する酸素遮蔽性の熱可塑性樹脂からなる中間層とを備えた外部層も、押出成形や共押出或いはサンドイッチラミネーションなどの通常の各種ラミネート法（積層法）により成形される。 Here, the inner layer sheet comprising the first layer and the second layer made of a thermoplastic resin and the intermediate layer made of a thermoplastic resin blended with an oxygen absorbent located between the two layers is formed by extrusion or coextrusion. Alternatively, it is molded by various ordinary laminating methods (lamination methods) such as sandwich lamination, and then composed of a third layer and a fourth layer made of a thermoplastic resin, and an oxygen-shielding thermoplastic resin located between the two layers. The outer layer including the intermediate layer is also formed by various ordinary laminating methods (laminating methods) such as extrusion molding, coextrusion, or sandwich lamination.
なお、従前の技術として、熱可塑性樹脂からなる内層及び外層と、内層側に位置する酸素吸収剤配合の熱可塑性樹脂からなる第１の中間層と、外層側に位置する酸素遮蔽性の熱可塑性樹脂からなる第２の中間層とを備えた多層成形容器における、多層シート成形材料の層構造の断面図が、図１に例示されている。
図中の上側が容器の外部で、図中の下側が容器の内部側に相当する。熱可塑性樹脂からなる内層及び外層（図中の白色部分）と、外層側に位置する酸素遮蔽性の熱可塑性樹脂からなる第２の中間層（図中の黒色部分）と、その両側の接着剤層（図示せず）と、内層側に位置する酸素吸収剤配合の熱可塑性樹脂からなる第１の中間層（図中のビーズ模様部分）が各々図示されている。Ａはシートの１次成形幅を、Ｂはシートの容器製品となる幅を、Ｃは酸素のバリア効果（酸素遮蔽ないし吸収効果）の有効幅を、Ｄはトリムロス幅（シートの両端屑の幅）を各々表わす。縦軸はシートの厚み（単位ｍｍ）を、横軸はシート中央部からの幅長さ（単位ｍｍ）を示す。図中にＡ〜Ｃのシート幅の１例がｍｍ単位で示されている。
As a conventional technique, an inner layer and an outer layer made of a thermoplastic resin, a first intermediate layer made of a thermoplastic resin blended with an oxygen absorbent located on the inner layer side, and an oxygen shielding thermoplastic located on the outer layer side A cross-sectional view of the layer structure of a multilayer sheet molding material in a multilayer molding container provided with a second intermediate layer made of resin is illustrated in FIG.
The upper side in the figure corresponds to the outside of the container, and the lower side in the figure corresponds to the inner side of the container. Inner layer and outer layer made of thermoplastic resin (white portion in the figure), second intermediate layer made of oxygen-shielding thermoplastic resin located on the outer layer side (black portion in the figure), and adhesive on both sides thereof A layer (not shown) and a first intermediate layer (bead pattern portion in the figure) made of a thermoplastic resin blended with an oxygen absorbent located on the inner layer side are shown. A is the primary forming width of the sheet, B is the width of the sheet container product, C is the effective width of the oxygen barrier effect (oxygen shielding or absorption effect), and D is the trim loss width (the width of scrap at both ends of the sheet) ) Respectively. The vertical axis represents the sheet thickness (unit: mm), and the horizontal axis represents the width (unit: mm) from the center of the sheet. In the drawing, one example of the sheet widths A to C is shown in mm.
このような多層成形容器における多層シート材料においては、同時多層押出し積層法などにより、多層シート材料を積層成形する際に、内層側に位置する酸素吸収剤配合の熱可塑性樹脂からなる第１の中間層において、鉄粉系などの酸素吸収剤の重量によってか、或いは、シートの層構成の対称性が乏しいためか、第１の中間層のシート中央部の層部分が図１に図示されるように垂れ下がってしまい、それに引かれて第２の中間層も垂れ下がり、そのためにシートの中間の各層がシートの中央部に引き寄せられ、酸素遮蔽層（第２の中間層）と酸素吸収層（第１の中間層）の層厚みが少ないか殆どなくて耐酸素性の機能が働かない部分がシートの両端にトリムロス（図中のＤ）として生じてしまう。また、そのためにバリア効果の有効幅（図中のＣ）も狭くなる。
そして、シートの中間の各層が垂れ下がることにより、シート層の構成が内外部において非対称となりシート層分布の成形安定性も悪くなってしまい、多層シート材料の積層成形における生産安定性が悪化しがちである。
更に、トリムロス中の酸素吸収剤は他の原料に比して高価なために、コストアップになってしまう問題も避けられない。
In the multilayer sheet material in such a multilayer molded container, when the multilayer sheet material is laminated and molded by a simultaneous multilayer extrusion lamination method or the like, a first intermediate composed of a thermoplastic resin blended with an oxygen absorbent located on the inner layer side. As shown in FIG. 1, the layer portion of the central portion of the first intermediate layer is illustrated in FIG. 1 depending on the weight of the oxygen absorbent such as iron powder in the layer, or because of the lack of symmetry in the layer structure of the sheet. And the second intermediate layer also hangs down due to that, so that each intermediate layer of the sheet is drawn to the center of the sheet, and the oxygen shielding layer (second intermediate layer) and the oxygen absorbing layer (first layer) The intermediate layer) has a small or almost no layer thickness and a portion where the oxygen resistance function does not work occurs as trim loss (D in the figure) at both ends of the sheet. For this reason, the effective width of the barrier effect (C in the figure) is also narrowed.
And, since each layer in the middle of the sheet hangs down, the configuration of the sheet layer becomes asymmetrical inside and outside, and the molding stability of the sheet layer distribution also deteriorates, and the production stability in the multilayer molding of the multilayer sheet material tends to deteriorate. is there.
Furthermore, since the oxygen absorbent in the trim loss is more expensive than other raw materials, the problem of increased costs is inevitable.
４．シートサイドトリム屑及びスケルトン屑の有効再利用
多層成形容器の材料となる多層成形シートの製造の際に、廃棄されるシートサイドトリム屑、及び容器成形時に生じるスケルトン屑を再利用の原料として、層形成の材料の一部とすれば、成形屑の再利用を実現できて、それにより多層容器の生産コストを低下できるばかりではなく、他層に比べて高価な酸素吸収剤配合の熱可塑性樹脂層屑の再利用により、生産コストをより有効に改善できる。また、回収された酸素吸収剤によって、酸素の吸収性と遮蔽性がより高められることも判明した。
そして驚くべきことに、多層シート材料を押出成形する際に、サイドトリム屑を混入した樹脂層を酸素遮蔽性熱可塑性樹脂層の外層側に設けると、酸素吸収性熱可塑性樹脂層がよりいっそう乱れず均一な層となり、サイドトリムの発生が大幅に低減されることも判明した。
4). Effective reuse of sheet-side trim scraps and skeleton scraps When manufacturing multilayer molded sheets that are the materials for multilayer molded containers, the sheet-side trim scraps that are discarded and the skeleton scraps generated during container molding are used as raw materials for recycling. If it is part of the forming material, it is possible not only to reduce the production cost of multi-layer containers by reusing molding waste, but also to add a more expensive oxygen absorbent compound layer compared to other layers. By reusing waste, production costs can be improved more effectively. It has also been found that the oxygen absorption and shielding properties can be further improved by the recovered oxygen absorbent.
Surprisingly, when extruding a multilayer sheet material, if a resin layer mixed with side trim debris is provided on the outer side of the oxygen-shielding thermoplastic resin layer, the oxygen-absorbing thermoplastic resin layer is further disturbed. It was also found that the layer was uniform and the occurrence of side trim was greatly reduced.
なお、上記の酸素吸収性熱可塑性樹脂層形成における新しい知見の応用として、廃棄されるシートサイドトリム屑及びスケルトン屑を他層に混入してもよい。
廃棄されるシートサイドトリム屑及びスケルトン屑を、酸素吸収性の中間層（オキシガード層）に混入して再使用することによって、内層側に位置する酸素吸収剤配合の熱可塑性樹脂からなる第１の中間層と、外層側に位置する酸素遮蔽性の熱可塑性樹脂からなる第２の中間層との成形安定性が向上して、シート中央部の層部分が垂れ下がってしまうことが解消されて、シートの中央部と両端部におけるシートの層構成が均一となり、シート両端のトリムロスの幅が大幅に減少し、さらにシート生産安定性も高まる。
In addition, as an application of the new knowledge in the above-described oxygen-absorbing thermoplastic resin layer formation, discarded sheet side trim waste and skeleton waste may be mixed in other layers.
The waste side-side trim scraps and skeleton scraps are mixed into the oxygen-absorbing intermediate layer (oxyguard layer) and reused, so that the first is made of a thermoplastic resin containing an oxygen absorbent positioned on the inner layer side. The molding stability of the intermediate layer and the second intermediate layer made of an oxygen-shielding thermoplastic resin located on the outer layer side is improved, and the layer portion at the center of the sheet is eliminated from sagging, The layer structure of the sheet at the center and both ends of the sheet is uniform, the width of trim loss at both ends of the sheet is greatly reduced, and sheet production stability is further improved.
このような、酸素吸収性熱可塑性樹脂層形成における新しい知見が、多層成形容器において利用され、第九発明の「熱可塑性樹脂からなる第１層及び第２層と、両層の中間に位置する酸素吸収剤配合の熱可塑性樹脂からなる中間層とを備えた内部層、及び、熱可塑性樹脂からなる第３層及び第４層と、両層の中間に位置する酸素遮蔽性の熱可塑性樹脂からなる中間層とを備えた外部層とからなり、酸素遮蔽性熱可塑性樹脂からなる中間層の外層側に、廃棄されるシートサイドトリム屑及びスケルトン屑が混入された層を更に設ける、又は酸素吸収剤配合の熱可塑性樹脂からなる中間層に、廃棄されるシートサイドトリム屑及びスケルトン屑が混入されることを特徴とする、酸素の吸収性と遮蔽性に優れた多層成形用シート。」の発明を構築している。 Such new knowledge in forming the oxygen-absorbing thermoplastic resin layer is utilized in the multilayer molded container, and “the first layer and the second layer made of a thermoplastic resin are positioned between the two layers in the ninth invention. From an inner layer provided with an intermediate layer made of a thermoplastic resin blended with an oxygen absorbent, a third layer and a fourth layer made of a thermoplastic resin, and an oxygen-shielding thermoplastic resin located between the two layers And an outer layer provided with an intermediate layer and an outer layer side of the intermediate layer made of oxygen-shielding thermoplastic resin, a layer mixed with discarded seat side trim scraps and skeleton scraps is further provided, or oxygen absorption A sheet for multilayer molding excellent in oxygen absorption and shielding properties, characterized in that discarded sheet side trim waste and skeleton waste are mixed in an intermediate layer made of a thermoplastic resin containing an agent. " Build There.
５．実施の態様としての発明
以上において詳しく述べた各々の基本的発明に対する実施の態様として、第四発明〜第六発明の、「酸素遮蔽性の熱可塑性樹脂からなる中間層の両側層に接着剤層が設けられたことを特徴とする、第一発明〜第三発明のいずれかにおける酸素の吸収性と遮蔽性に優れた多層成形容器」、「第１層〜第４層の熱可塑性樹脂がポリプロピレン系樹脂であり、酸素遮蔽性の熱可塑性樹脂がエチレン−ビニルアルコール共重合体であり、酸素吸収剤配合の熱可塑性樹脂がポリオレフィン系樹脂であることを特徴とする、第一発明〜第三発明のいずれかにおける酸素の吸収性と遮蔽性に優れた多層成形容器」、及び「酸素吸収剤が鉄系脱酸素剤であることを特徴とする、第一発明〜第五発明のいずれかにおける酸素の吸収性と遮蔽性に優れた多層成形容器」がある。
5. Inventions as Embodiments As embodiments for each of the basic inventions described in detail above, according to the fourth to sixth inventions, “adhesive layers on both side layers of an intermediate layer made of an oxygen-shielding thermoplastic resin” A multilayer molded container excellent in oxygen absorption and shielding properties in any one of the first to third inventions, "the first to fourth layer thermoplastic resins are polypropylene. First invention to third invention, characterized in that the oxygen-shielding thermoplastic resin is an ethylene-vinyl alcohol copolymer, and the oxygen-absorbing thermoplastic resin is a polyolefin resin. And the oxygen absorber according to any one of the first to fifth inventions, wherein the oxygen absorbent is an iron-based oxygen absorber. Absorption and shielding There is a “multilayer molded container having excellent opacity”.
第四発明は、酸素遮蔽性の第２の中間層の両側層に接着剤層が設けられることを特徴とするもので、接着剤は任意使用であり、第一の中間層と両側層との接合性が悪い場合に使用される。通常は、第２の中間層の酸素遮蔽性の熱可塑性樹脂にエチレン−ビニルアルコール共重合体が使用され、両側層に汎用されるポリプロピレン系樹脂との接着性がよくないので、汎用接着剤であるエチレン−アクリル酸エステル共重合体などの熱可塑性樹脂接着剤が用いられる。
その他の接着剤の適当な例は、エチレン−アクリル酸共重合体、イオン架橋オレフィン共重合体、無水マレイン酸グラフトポリエチレン、無水マレイン酸グラフトポリプロピレン、アクリル酸グラフトポリプロピレン、エチレン−酢酸ビニル共重合体、共重合ポリエステル、共重合ポリアミドなどの１種又は２種以上の組み合わせである。これらの接着剤樹脂は、同時押出或いはサンドイッチラミネーションなどによる積層に有用である。
The fourth invention is characterized in that an adhesive layer is provided on both side layers of the oxygen-shielding second intermediate layer, the adhesive is optional, and the first intermediate layer and both side layers Used when the bondability is poor. Usually, an ethylene-vinyl alcohol copolymer is used for the oxygen-shielding thermoplastic resin of the second intermediate layer, and the adhesiveness with a polypropylene resin generally used for both side layers is not good. A thermoplastic resin adhesive such as an ethylene-acrylic acid ester copolymer is used.
Suitable examples of other adhesives include ethylene-acrylic acid copolymer, ion-crosslinked olefin copolymer, maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, acrylic acid grafted polypropylene, ethylene-vinyl acetate copolymer, One type or a combination of two or more types such as a copolyester and a copolyamide. These adhesive resins are useful for lamination by coextrusion or sandwich lamination.
第五発明は、使用される樹脂の具体例を示すもので、第１層〜第４層の熱可塑性樹脂がポリプロピレン系樹脂であり、第１の中間層の熱可塑性樹脂がポリオレフィン系樹脂であって、第２の中間層の酸素遮蔽性の熱可塑性樹脂がエチレン−ビニルアルコール共重合体である。
ポリプロピレン系樹脂は、その耐衝撃性などの機械的物性や耐薬品性などの化学的物性に優れており、成形性や経済性も卓越で、酸素遮蔽性も備えているから、内層及び外層の熱可塑性樹脂として汎用される。なお、最内層の樹脂としては容器内部の酸素吸収のためにある程度の酸素透過性を有するポリオレフィン系樹脂がより好ましい。ポリプロピレン系樹脂としては、具体的に、アイソタクティックポリプロピレン、エチレン−プロピレン共重合体、プロピレン−ブテン−１共重合体、及びこれらのブレンド物が使用される。これらのポリプロピレン系樹脂は、通常、第１の中間層に配合されている鉄系脱酸素剤の黒色を隠蔽するために、酸化チタンなどの白色顔料を配合した組成物の形で使用に供される。
The fifth invention shows a specific example of the resin used, wherein the thermoplastic resin of the first layer to the fourth layer is a polypropylene resin, and the thermoplastic resin of the first intermediate layer is a polyolefin resin. The oxygen-shielding thermoplastic resin of the second intermediate layer is an ethylene-vinyl alcohol copolymer.
Polypropylene resin is excellent in mechanical properties such as impact resistance and chemical properties such as chemical resistance, has excellent moldability and economy, and has oxygen shielding properties. Widely used as a thermoplastic resin. The innermost layer resin is more preferably a polyolefin resin having a certain degree of oxygen permeability for oxygen absorption inside the container. Specific examples of the polypropylene resin include isotactic polypropylene, ethylene-propylene copolymer, propylene-butene-1 copolymer, and blends thereof. These polypropylene resins are usually used in the form of a composition containing a white pigment such as titanium oxide in order to conceal the black color of the iron-based oxygen absorber contained in the first intermediate layer. The
第１の中間層の熱可塑性樹脂としては、容器内部の酸素吸収のためにある程度の酸素透過性を有するポリオレフィン系樹脂が汎用される。また、ポリプロピレン系樹脂からなる内層及び外層は、水分の透過を抑制し、エチレン−ビニルアルコール共重合体の吸湿による酸素遮蔽性の低下を抑制する。
第２の中間層の酸素遮蔽性の熱可塑性樹脂としてのエチレン−ビニルアルコール共重合体も、その優れた酸素遮蔽性により汎用され、エチレン−ビニルアルコール共重合体の具体例としては、エチレン−酢酸ビニル共重合体を、ケン化度が９６モル％以上、特に９９モル％以上となるようにケン化して得られる共重合体ケン化物が使用される。
As the thermoplastic resin of the first intermediate layer, a polyolefin resin having a certain degree of oxygen permeability for absorbing oxygen inside the container is generally used. In addition, the inner layer and the outer layer made of polypropylene resin suppress moisture permeation and suppress a decrease in oxygen shielding property due to moisture absorption of the ethylene-vinyl alcohol copolymer.
An ethylene-vinyl alcohol copolymer as an oxygen-shielding thermoplastic resin for the second intermediate layer is also widely used due to its excellent oxygen-shielding property. As a specific example of the ethylene-vinyl alcohol copolymer, ethylene-acetic acid is used. A saponified copolymer obtained by saponifying a vinyl copolymer so as to have a saponification degree of 96 mol% or more, particularly 99 mol% or more is used.
第六発明は、酸素吸収剤が鉄系脱酸素剤であることを特徴とするもので、酸素吸収性と経済性に優れた代表的な酸素吸収剤（脱酸素剤）を例示している。
鉄系脱酸素剤は、その優れた還元性（周囲物質からの脱酸素性）により強力な酸素吸収作用をもたらす。
なお、鉄系脱酸素剤としては、従来この種の用途に使用されているものは全て使用することができ、例えば還元性鉄、酸化第一鉄、四三酸化鉄、炭化鉄、ケイ素鉄、鉄カルボニル、水酸化鉄などを例示できる。これらは１種単独でも２種以上を組み合わせても使用することができる。粒径や密度も通常のものが好適である。あまり平均粒径が大きいものを使用すると、多層シートへの成形に際してフィッシュアイなどが発生し、容器の外観が損なわれることがある。
鉄系脱酸素剤は、一般に樹脂当り１〜２００重量％、特に１０〜１００重量％の量とすることが好適である。鉄系脱酸素剤の量が上記範囲よりも少ないと、容器内の酸素濃度を微生物の成育に適した濃度以下に抑制することが困難となり、一方上記範囲よりも多量に用いたとしても、酸素濃度低下の点で格別の効果がないばかりか、成形性や価格の点で不利となる傾向がある。
The sixth invention is characterized in that the oxygen absorber is an iron-based oxygen absorber, and exemplifies a typical oxygen absorber (oxygen absorber) excellent in oxygen absorption and economy.
The iron-based oxygen absorber provides a strong oxygen absorbing action due to its excellent reducibility (deoxygenation from surrounding substances).
In addition, as an iron-type oxygen absorber, what was conventionally used for this kind of application can be used, for example, reducing iron, ferrous oxide, iron tetroxide, iron carbide, silicon iron, Examples thereof include iron carbonyl and iron hydroxide. These can be used singly or in combination of two or more. The normal particle size and density are also suitable. If a material having an excessively large average particle diameter is used, fish eyes and the like may be generated during forming into a multilayer sheet, and the appearance of the container may be impaired.
In general, the iron-based oxygen scavenger is preferably 1 to 200% by weight, particularly 10 to 100% by weight per resin. If the amount of the iron-based oxygen scavenger is less than the above range, it will be difficult to control the oxygen concentration in the container below the concentration suitable for the growth of microorganisms. Not only is there no particular effect in terms of concentration reduction, but there is a tendency to be disadvantageous in terms of formability and price.
以下において、実施例により本発明をより具体的に提示して、比較例との対照により、本発明の構成の合理性と有意性を実証する。
〔実施例〕
本実施例は、基本的発明である第一発明を対象とするものであり、『熱可塑性樹脂からなる第１層及び第２層と、両層の中間に位置する酸素吸収剤配合の熱可塑性樹脂からなる中間層とを備えた内部層、及び、熱可塑性樹脂からなる第３層及び第４層と、両層の中間に位置する酸素遮蔽性の熱可塑性樹脂からなる中間層とを備えた外部層とからなることを特徴とする、酸素の吸収性と遮蔽性に優れた、深絞り成形による多層成形容器』に係るものである。
In the following, the present invention will be presented more specifically by way of examples, and the rationality and significance of the configuration of the present invention will be demonstrated by contrast with comparative examples.
〔Example〕
The present embodiment is directed to the first invention which is a basic invention, and “the first layer and the second layer made of a thermoplastic resin and a thermoplastic compounded with an oxygen absorbent located between the two layers. An inner layer provided with an intermediate layer made of a resin, a third layer and a fourth layer made of a thermoplastic resin, and an intermediate layer made of an oxygen-shielding thermoplastic resin located between the two layers The present invention relates to a multilayer molded container by deep drawing excellent in oxygen absorption and shielding properties, characterized by comprising an outer layer.
［図による例示］
実施例に関わる多層成形容器及び多層厚肉シート材料の層構成の実例が、図２に図示されている。
なお、前述のとおり、図中の上側が容器の外部で、図中の下側が容器の内部側に相当する。熱可塑性樹脂からなる第１層〜第４層は、１１と１３と１４と１７であり、内層側に位置する酸素吸収剤配合の熱可塑性樹脂からなる中間層は１２であり、外層側に位置する酸素遮蔽性の熱可塑性樹脂からなる中間層は１６であり、その両側の接着剤層は１５である。
[Exemplary illustration]
An example of the layer configuration of the multilayer molded container and multilayer thick sheet material according to the example is illustrated in FIG.
As described above, the upper side in the figure corresponds to the outside of the container, and the lower side in the figure corresponds to the inner side of the container. The first to fourth layers made of thermoplastic resin are 11, 13, 14, and 17, and the intermediate layer made of a thermoplastic resin blended with an oxygen absorbent located on the inner layer side is 12 and is located on the outer layer side. The intermediate layer made of oxygen-shielding thermoplastic resin is 16, and the adhesive layers on both sides thereof are 15.
［多層シート材料の製造］
第１層〜第４層の熱可塑性樹脂として、プロピレン−エチレンブロック共重合体、第１の中間層として、プロピレン−エチレンランダム共重合体とその樹脂１００重量部当たり３７重量部の鉄系脱酸素剤を含有する組成物を使用し、第２の中間層として、エチレン−ビニルアルコール共重合体をそれぞれ使用し、先ず共押し出しによって、内部層を成形してから外部層を積層して、多層シート材料を成形した。なお、エチレン−ビニルアルコール共重合体とこれに隣接する層との間には接着剤樹脂層が形成されるようにして多層同時共押出を行った。
[Manufacture of multilayer sheet materials]
The first to fourth thermoplastic resins are propylene-ethylene block copolymers, and the first intermediate layer is propylene-ethylene random copolymer and 37 parts by weight of iron-based deoxygenated per 100 parts by weight of the resin. A composition containing an agent, an ethylene-vinyl alcohol copolymer is used as the second intermediate layer, the inner layer is first molded by coextrusion, and then the outer layer is laminated. The material was molded. In addition, multilayer co-extrusion was performed so that an adhesive resin layer was formed between the ethylene-vinyl alcohol copolymer and a layer adjacent thereto.
［多層容器の製造］
通常の真空圧空成形機で、多数個取り金型を用いて深絞り成形を行い、口外径７５ｍｍ・高さ９４ｍｍ・内容量２２５ｍｌの多層深絞り容器を成形した。
[Manufacture of multilayer containers]
Using an ordinary vacuum / pressure forming machine, deep drawing was performed using a multi-cavity mold to form a multilayer deep drawing container having a mouth outer diameter of 75 mm, a height of 94 mm, and an inner volume of 225 ml.
［結果］
第２の中間層の垂れ下がりは殆ど生じず、シートの中央部と両端部におけるシートの層構成が大略均一となった。
[result]
The second intermediate layer was hardly dripped, and the sheet layer configuration at the center and both ends of the sheet was substantially uniform.
〔比較例〕
実施例において全層を共押出しにより同時押出成形した以外は、実施例と全く同様にして多層厚肉シート材料及び多層容器の製造を行った。
[Comparative example]
In the examples, a multilayer thick sheet material and a multilayer container were produced in exactly the same manner as in the examples except that all layers were coextruded by coextrusion.
［結果］
多層厚肉シート材料においては、図１に示される以上に、第２の中間層の垂れ下がりが生じ、シートの中央部と両端部におけるシートの層構成が乱れ不均一となり、多層容器の成形には不適当なものであった。実施例と比較例の結果を表１に掲示する。
[result]
In the multilayer thick sheet material, the second intermediate layer sags more than shown in FIG. 1, and the sheet layer configuration at the center and both ends of the sheet becomes disordered and non-uniform. It was inappropriate. The results of Examples and Comparative Examples are shown in Table 1.
［実施例と比較例の結果の考察］
以上の実施例及び比較例を対照することにより、本発明では、多層厚肉シート材料において、シートサイドトリム量が従前（比較例）に比べて大幅に減少し、多層シート材料の中間層の垂れ下がりも発生せず、酸素吸収剤配合の中間層の均一形成によるシートサイドトリム料の僅少によって、コストダウンへの寄与が大きくなっている。そして、本発明では、多層成形容器において、酸素遮蔽性及び吸収性が高く、内容物保存容器として食品の保存が味と香りにおいて非常に優れていることが明らかにされている。
したがって、本発明の構成の合理性と有意性及び従来技術への卓越性が明らかにされている。
[Consideration of results of Examples and Comparative Examples]
By contrasting the above examples and comparative examples, in the present invention, in the multilayer thick sheet material, the amount of sheet side trim is greatly reduced compared to the conventional (comparative example), and the intermediate layer of the multilayer sheet material hangs down. The amount of seat side trim due to the uniform formation of the intermediate layer containing the oxygen absorbent is small, and the contribution to cost reduction is increasing. And in this invention, in a multilayer molded container, oxygen shielding property and absorptivity are high, and it is clarified that the preservation | save of a foodstuff is very excellent in a taste and fragrance as a content storage container.
Therefore, the rationality and significance of the configuration of the present invention and the superiority to the prior art are clarified.
Ａ： シートの１次成形幅 Ｂ： シートの容器製品となる幅
Ｃ： 酸素のバリア効果の有効幅 Ｄ： トリムロス幅
１１：熱可塑性樹脂からなる第１層
１２：内層側に位置する酸素吸収剤配合の熱可塑性樹脂からなる中間層
１３：熱可塑性樹脂からなる第２層
１４：熱可塑性樹脂からなる第３層
１５：接着剤層
１６：外層側に位置する酸素遮蔽性の熱可塑性樹脂からなる中間層
１７：熱可塑性樹脂からなる第４層
A: Primary forming width of sheet B: Width of sheet product C: Effective width of oxygen barrier effect D: Trim loss width 11: First layer made of thermoplastic resin 12: Oxygen absorbent located on inner layer side Intermediate layer 13 made of blended thermoplastic resin: Second layer made of thermoplastic resin 14: Third layer made of thermoplastic resin 15: Adhesive layer 16: Made of oxygen-shielding thermoplastic resin located on the outer layer side Intermediate layer 17: fourth layer made of thermoplastic resin
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| ES2358707A1 (en) * | 2009-10-16 | 2011-05-13 | Repsol Ypf S.A. | Polypropylene polymer composition that can absorb oxygen |
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| JPH10248541A (en) * | 1997-03-13 | 1998-09-22 | Mitsubishi Gas Chem Co Inc | Preservation of prepared-dishes |
| JPH10257862A (en) * | 1997-03-19 | 1998-09-29 | Mitsubishi Gas Chem Co Inc | Preservation of cooked rice and packaged body |
| JPH10329276A (en) * | 1997-06-04 | 1998-12-15 | Mitsubishi Gas Chem Co Inc | Deoxidizing multilayer material, packaging vessel constituted thereof, and method for preservation of foodstuff or pharmaceutical |
| JPH1148385A (en) * | 1997-08-06 | 1999-02-23 | Mitsubishi Gas Chem Co Inc | Deoxidizable multilayer container |
| JPH11151783A (en) * | 1997-11-21 | 1999-06-08 | Kishimoto Akira | Packing laminate containing activation type oxygen absorbent |
| JP2000037823A (en) * | 1998-07-27 | 2000-02-08 | Ajinomoto Co Inc | Sheet like laminated material and container using the same |
| JP4120723B2 (en) * | 1998-08-13 | 2008-07-16 | 三菱瓦斯化学株式会社 | Deoxygenating multilayer film and method for producing the same |
| JP2002036463A (en) * | 2000-07-19 | 2002-02-05 | Toyo Seikan Kaisha Ltd | Oxygen absorbable laminate |
| JP2002145351A (en) * | 2000-11-10 | 2002-05-22 | Toyo Seikan Kaisha Ltd | Oxygen absorbing plastic container |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2358707A1 (en) * | 2009-10-16 | 2011-05-13 | Repsol Ypf S.A. | Polypropylene polymer composition that can absorb oxygen |
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| JP4737649B2 (en) | 2011-08-03 |
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