JP2014213934A - Container - Google Patents
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- JP2014213934A JP2014213934A JP2013095446A JP2013095446A JP2014213934A JP 2014213934 A JP2014213934 A JP 2014213934A JP 2013095446 A JP2013095446 A JP 2013095446A JP 2013095446 A JP2013095446 A JP 2013095446A JP 2014213934 A JP2014213934 A JP 2014213934A
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- -1 polypropylene Polymers 0.000 claims abstract description 67
- 239000004698 Polyethylene Substances 0.000 claims abstract description 54
- 229920001971 elastomer Polymers 0.000 claims abstract description 45
- 239000000806 elastomer Substances 0.000 claims abstract description 43
- 239000004743 Polypropylene Substances 0.000 claims abstract description 42
- 229920000573 polyethylene Polymers 0.000 claims abstract description 36
- 229920001155 polypropylene Polymers 0.000 claims abstract description 32
- 229920001684 low density polyethylene Polymers 0.000 claims abstract description 25
- 239000004702 low-density polyethylene Substances 0.000 claims abstract description 25
- 229920003023 plastic Polymers 0.000 claims abstract description 16
- 239000004033 plastic Substances 0.000 claims abstract description 16
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 7
- 230000004888 barrier function Effects 0.000 claims description 7
- 239000000203 mixture Substances 0.000 abstract description 25
- 239000010410 layer Substances 0.000 description 53
- 230000000052 comparative effect Effects 0.000 description 19
- 229920000092 linear low density polyethylene Polymers 0.000 description 13
- 239000004707 linear low-density polyethylene Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 239000011342 resin composition Substances 0.000 description 10
- 238000009472 formulation Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 239000012790 adhesive layer Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920005604 random copolymer Polymers 0.000 description 3
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 238000000071 blow moulding Methods 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 235000011194 food seasoning agent Nutrition 0.000 description 2
- 235000008960 ketchup Nutrition 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 235000015067 sauces Nutrition 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 239000004278 EU approved seasoning Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920006038 crystalline resin Polymers 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000010746 mayonnaise Nutrition 0.000 description 1
- 239000008268 mayonnaise Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 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
- 239000000126 substance Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B1/00—Layered products having a general shape other than plane
- B32B1/08—Tubular products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
- B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
- B65D1/0207—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features
- B65D1/0215—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features multilayered
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
Abstract
Description
本発明は、プラスチック容器に関し、特に食品用のボトルに関する。さらにいえば、耐低温衝撃性を有し、耐熱剛性が大きく、熱充填に適したポリプロピレンを使用したものに関する。 The present invention relates to a plastic container, and more particularly to a food bottle. More specifically, the present invention relates to a material using polypropylene that has low temperature impact resistance, high heat resistance rigidity, and suitable for heat filling.
本発明に関連する技術が記載された文献として、特許文献1ないし4をあげる。特許文献1は、プラスチック容器の先行例であり、ポリプロピレン樹脂に直鎖状ポリエチレンをブレンドさせた樹脂組成物により、耐低温衝撃性をポリプロピレン単体より向上させることについて記載がある。尚、耐低温衝撃性とは、冷蔵庫内の温度を想定した摂氏5℃未満の低温での破損を防ぐという評価方法を用いた容器物性の一指標である。耐低温衝撃性が高い容器ほど、低温での破損が小さい。
特許文献2、3には、ポリプロピレンと直鎖状ポリエチレンと低密度ポリエチレンの組成物を用いることにより、耐低温衝撃性をポリプロピレン単体より向上させることについての記載がある。 Patent Documents 2 and 3 describe that low-temperature impact resistance is improved from that of polypropylene alone by using a composition of polypropylene, linear polyethylene, and low-density polyethylene.
特許文献4には、ポリプロピレンにスチレン−ブタジエンランダム共重合体の水素添加ポリマーを含有させることによって、耐低温衝撃性と透明性をポリプロピレン単体より向上させること、また、そのようにして得られた樹脂組成物を主層(最も厚い層)に用いることについて記載がある(特許文献4の段落0017参照)。 Patent Document 4 discloses that by adding a hydrogenated polymer of a styrene-butadiene random copolymer to polypropylene, the low-temperature impact resistance and transparency are improved as compared with polypropylene alone, and the resin thus obtained There is a description about using the composition for the main layer (thickest layer) (see paragraph 0017 of Patent Document 4).
従来のポリプロピレンに直鎖状ポリエチレンまたは低密度ポリエチレンをブレンドさせて低温衝撃強度を向上させる技術では、十分な改質強度を得るために直鎖状ポリエチレンや低密度ポリエチレンを多量に持ちいらなければならず、主材のポリプロピレンの透明性や耐熱剛性が損なわれる点で問題になる。また、ポリプロピレンにスチレン−ブタジエンランダム共重合体の水素添加ポリマーを含有させると耐低温衝撃性と透明性をポリプロピレン単体より向上させることが出来るものの耐熱剛性が低下する点で問題となる。 In conventional techniques to improve low-temperature impact strength by blending linear polyethylene or low-density polyethylene with polypropylene, a large amount of linear polyethylene or low-density polyethylene must be carried to obtain sufficient modified strength. However, there is a problem in that the transparency and heat-resistant rigidity of the main polypropylene are impaired. In addition, when a hydrogenated polymer of a styrene-butadiene random copolymer is contained in polypropylene, although low temperature impact resistance and transparency can be improved from polypropylene alone, there is a problem in that the heat resistance rigidity is lowered.
耐熱剛性とは、80℃程度の高温時における容器の剛性に関する指標である。調味料の中でも高粘度の調味料を充填する際に、粘度調整の目的で80℃近辺の温度で充填することがある。その際の充填の熱によって、容器の剛性が低下し充填ラインにて取扱いにくくなることを防止する必要がある。従って、80℃時の引張弾性率を測定し評価する。 The heat-resistant rigidity is an index related to the rigidity of the container at a high temperature of about 80 ° C. When filling a high-viscosity seasoning among seasonings, it may be filled at a temperature around 80 ° C. for the purpose of adjusting the viscosity. It is necessary to prevent the rigidity of the container from being lowered and difficult to handle in the filling line due to the heat of filling at that time. Therefore, the tensile elastic modulus at 80 ° C. is measured and evaluated.
本発明は、上記実情に鑑みてなされたものであって、耐低温衝撃性及び耐熱剛性に優れた透明性の高い容器を提供することを目的とする。 This invention is made | formed in view of the said situation, Comprising: It aims at providing the highly transparent container excellent in low temperature impact resistance and heat-resistant rigidity.
本発明者らは、上記課題を達成するべく検討を重ねた結果、以下の構成をもって、上記の目的を達成できることを見出し、本発明を完成するに至った。 As a result of repeated studies to achieve the above problems, the present inventors have found that the above object can be achieved with the following configuration, and have completed the present invention.
容器の少なくとも1つの層に、ポリプロピレンと、直鎖状ポリエチレンと、低密度ポリエチレンと、ポリエチレン系エラストマーとを配する混合層を持つプラスチック容器を使用する。 A plastic container having a mixed layer in which polypropylene, linear polyethylene, low-density polyethylene, and a polyethylene-based elastomer are arranged is used in at least one layer of the container.
本発明によれば、低温耐衝撃性及び耐熱剛性に優れた透明性の高い容器を提供することが可能となる。 According to the present invention, it is possible to provide a highly transparent container excellent in low-temperature impact resistance and heat-resistant rigidity.
本実施形態の多層プラスチック容器は、内容物を高温で充填される容器であって、少なくとも1層が、ポリプロピレンと、ポリエチレン系エラストマーと、直鎖状ポリエチレンと低密度ポリエチレンの混合物からなる層を有することを特徴とする。ここで、ポリエチレン系エラストマーとは、ポリエチレンをハードセグメントとして、所定のゴム成分をソフトセグメントとしたエラストマーをいう。例えば、エチレンに対してコモノマーとしてブテンを入れたC−4のポリエチレン系エラストマー、ヘキセンを入れたC−6のポリエチレン系エラストマー、オクテンをいれたC−8のポリエチレン系エラストマーなどが挙げられる。 The multilayer plastic container of the present embodiment is a container filled with the contents at a high temperature, and at least one layer has a layer made of a mixture of polypropylene, polyethylene elastomer, linear polyethylene and low density polyethylene. It is characterized by that. Here, the polyethylene elastomer refers to an elastomer having polyethylene as a hard segment and a predetermined rubber component as a soft segment. For example, C-4 polyethylene elastomer containing butene as a comonomer with respect to ethylene, C-6 polyethylene elastomer containing hexene, C-8 polyethylene elastomer containing octene, and the like.
本実施形態の多層プラスチック容器としては、図1に見られるような中空ボトルをはじめとする各種形状の容器が挙げられ、これらのプラスチック容器は、ロータリーブロー成形、シャトル方式のブロー成形等の方法により製造することができる。 Examples of the multilayer plastic container of this embodiment include containers of various shapes including hollow bottles as seen in FIG. 1, and these plastic containers can be produced by a method such as rotary blow molding or shuttle blow molding. Can be manufactured.
本実施形態の多層プラスチック容器は、例えば、ケチャップ、マヨネーズ、ソース等の食品用ボトルとして有用である。特に、ケチャップ、ソースのように常温では高粘度であるが高温時には低粘度になる特性を持っている流体には、高温で充填する必要があるため、本実施形態容器を使用することにより、容器が変形せずライン適性が低下しないため生産効率がプロピレン単体多層容器と比較して向上する。 The multilayer plastic container of this embodiment is useful as a food bottle such as ketchup, mayonnaise, sauce, and the like. In particular, a fluid having a characteristic of high viscosity at normal temperature but low viscosity at high temperature such as ketchup and sauce needs to be filled at high temperature. As a result, the production efficiency is improved as compared with a propylene simple substance multilayer container.
図2に、図1のプラスチック容器のA部の層構成の好適な1例を示す。図2に示した層構成においては、外層2(混合層)、接着層3、ガスバリア層4、接着層3、中間層5、内層6(混合層)が、この順番で積層された層構成である。外層2、内層6は、耐低温衝撃性、耐熱剛性に優れるポリプロピレンと、直鎖状ポリエチレンと低密度ポリエチレンとポリエチレン系エラストマーの混合物を使用する。具体的には、ポリプロピレン/直鎖状ポリエチレン/低密度ポリエチレン/ポリエチレン系エラストマー=84.6/9.4/1/5の割合が好ましい。接着層3としては、無水マレイン酸グラフトポリプロピレンなどの接着樹脂を使用する。ガスバリア層4として、エチレン酢酸ビニル共重合体(EVOH)からなるガスバリア層を使用する。中間層5としては、プラスチック容器の成形時に発生するバリなどのスクラップ樹脂、またはスクラップ樹脂と未使用のポリプロピレンをブレンドした混合樹脂などを使用することが出来る。 FIG. 2 shows a preferred example of the layer configuration of part A of the plastic container of FIG. In the layer configuration shown in FIG. 2, the outer layer 2 (mixed layer), the adhesive layer 3, the gas barrier layer 4, the adhesive layer 3, the intermediate layer 5, and the inner layer 6 (mixed layer) are stacked in this order. is there. The outer layer 2 and the inner layer 6 use a mixture of polypropylene excellent in low-temperature impact resistance and heat-resistant rigidity, linear polyethylene, low-density polyethylene and polyethylene-based elastomer. Specifically, a ratio of polypropylene / linear polyethylene / low density polyethylene / polyethylene elastomer = 84.6 / 9.4 / 1/5 is preferable. As the adhesive layer 3, an adhesive resin such as maleic anhydride grafted polypropylene is used. As the gas barrier layer 4, a gas barrier layer made of an ethylene vinyl acetate copolymer (EVOH) is used. As the intermediate layer 5, scrap resin such as burrs generated at the time of molding a plastic container or a mixed resin obtained by blending scrap resin and unused polypropylene can be used.
ガスバリア層とは、エチレン酢酸ビニル共重合体(EVOH)やポリアミドなどの主材のポリオレフィンと比較し気体透過性の小さい樹脂を用いて、酸素に代表される食品の風味を低下させる気体を遮断する層のことである。 A gas barrier layer uses a resin that has a lower gas permeability compared to polyolefin, which is a main material such as ethylene-vinyl acetate copolymer (EVOH) and polyamide, and blocks gas that lowers the flavor of food typified by oxygen. It is a layer.
図2に示した層構成を持つ容器に配置される最適な膜比率は外層2(混合層)、内層6(混合層)を合わせて容器全体の厚みに対して20%以上である。そのことにより。低温耐衝撃性及び耐熱剛性に優れた多層容器が作製できる。ここで、容器全体の厚みは、マイクロメーターを使い、容器の全域にわたって、容器高さ方向10mmごと、容器周方向10mmごとに厚みを測定し、平均して求める。また、外層2、内層6の厚みは、容器全高の1/2高さ位置にて周方向12方向で切出し、ミクロトームで切削した薄片を光学顕微鏡を用いて目視で測定した数値の平均値にて得られる。本実施形態においては、容器全体の厚みは、0.6mmであり、外層2、内層6を合算した層の厚みは、120μm以上である。 The optimum film ratio to be disposed in the container having the layer configuration shown in FIG. 2 is 20% or more of the total thickness of the container including the outer layer 2 (mixed layer) and the inner layer 6 (mixed layer). By that. A multilayer container excellent in low temperature impact resistance and heat resistance rigidity can be produced. Here, the thickness of the entire container is obtained by measuring the thickness for every 10 mm in the container height direction and for every 10 mm in the container circumferential direction over the entire area of the container and averaging it. Further, the thicknesses of the outer layer 2 and the inner layer 6 are the average values of numerical values obtained by measuring the slices cut in the circumferential direction 12 at a half height position of the total height of the container and cutting with a microtome using an optical microscope. can get. In the present embodiment, the total thickness of the container is 0.6 mm, and the total thickness of the outer layer 2 and the inner layer 6 is 120 μm or more.
例えば、先ほど示した肉厚0.6mmの容器であれば、外層2(混合層)は141μm、接着層3(外層側)7.5μm、ガスバリア層4は24μm、接着層3(内層側)7.5μm、中間層5は240μm、内層6(混合層)は180μmのように配置することが望ましい。 For example, in the case of a container having a thickness of 0.6 mm as shown above, the outer layer 2 (mixed layer) is 141 μm, the adhesive layer 3 (outer layer side) 7.5 μm, the gas barrier layer 4 is 24 μm, and the adhesive layer 3 (inner layer side) 7 5 μm, the intermediate layer 5 is preferably 240 μm, and the inner layer 6 (mixed layer) is preferably 180 μm.
この樹脂組成物の主成分であるポリプロピレンは、エチレン−プロピレン・ランダム共重合体(r−PP)であることが透明性の点で好ましい。 The polypropylene as the main component of the resin composition is preferably an ethylene-propylene / random copolymer (r-PP) from the viewpoint of transparency.
また、以下の実施例に示すように、ポリプロピレンの総量は、透明性、耐熱剛性の観点より70重量%以上が好ましい。さらに、好ましい範囲は、高い水準の耐熱剛性を求める点で80%以上、耐低温衝撃性の関係から90%未満が好ましい。 Further, as shown in the following examples, the total amount of polypropylene is preferably 70% by weight or more from the viewpoint of transparency and heat-resistant rigidity. Further, the preferable range is 80% or more from the viewpoint of obtaining a high level of heat resistance rigidity, and less than 90% from the viewpoint of low temperature impact resistance.
[実施例]
以下、本発明の内外層材(外層2、内層6いずれも混合層)として使用する材料構成の実施例と比較例について説明を行う。多層容器とは、各層の多層構造であるので、それぞれの層にそれぞれの機能を持たせている。基本的には、内外層材に、耐低温衝撃性、耐熱剛性、透明性の機能を持たせているため、内外層材の物性を評価することにより、多層容器の耐低温衝撃性、耐熱剛性、透明性の評価につながる。なお、以下の例においては、厚さ1.5mm、幅25mmのシートを成形し評価を行った。
[Example]
Hereinafter, examples and comparative examples of material configurations used as the inner and outer layer materials of the present invention (both outer layer 2 and inner layer 6 are mixed layers) will be described. Since the multilayer container is a multilayer structure of each layer, each layer has a function. Basically, because the inner and outer layer materials have the functions of low temperature shock resistance, heat resistance rigidity, and transparency, the low temperature shock resistance and heat resistance rigidity of the multilayer container are evaluated by evaluating the physical properties of the inner and outer layer materials. , Leading to transparency evaluation. In the following examples, a sheet having a thickness of 1.5 mm and a width of 25 mm was formed and evaluated.
[材料構成]
ポリプロピレン(PP)と、ポリエチレン系エラストマー(PE系エラストマー)、直鎖状低密度ポリエチレン(LLDPE)と、低密度ポリエチレン(LDPE)の配合を種々に変更して試行し、下記の実施例1と比較例1ないし5を得た。
[Material composition]
Experiments were made with various combinations of polypropylene (PP), polyethylene elastomer (PE elastomer), linear low density polyethylene (LLDPE), and low density polyethylene (LDPE), and compared with Example 1 below. Examples 1 to 5 were obtained.
[実施例1]
混合物合計100重量%として、ランダムポリプロピレン(r−PP 密度:0.890g/cm3、MFR(230℃、2.16kg):1.20g/10min、融点:135℃)を84.6重量%用い、直鎖状低密度ポリエチレン(LLDPE 密度:0.898g/cm3、MFR(190℃、2.16kg):2.00g/10min、融点:94℃)を9.4重量%と、低密度ポリエチレン(LDPE 密度:0.923g/cm3、MFR(190℃、2.16kg):0.60g/10min、融点:112℃)を1重量%と、ポリエチレン系エラストマー(PE系エラストマー1(コモノマーは1−ブテン) 密度0.860g/cm3、MFR(190℃、2.16kg):0.50g/10min、融点50℃)5重量%を配合して混練し、得られた樹脂組成物の23℃での透明性、80℃での耐熱剛性、−5℃の低温衝撃性についての評価を行った。物性値の密度、MFRは、JIS K 7112に基づき測定し、融点はDSCのピークから判断した。また、実施例1の配合を具体的な割合で示すと以下のようになる。r−PP/LLDPE/LDPE/PE系エラストマー1=84.6/9.4/1/5
[Example 1]
84.6% by weight of random polypropylene (r-PP density: 0.890 g / cm 3 , MFR (230 ° C., 2.16 kg): 1.20 g / 10 min, melting point: 135 ° C.) is used as the total mixture of 100% by weight. 9.4% by weight of linear low density polyethylene (LLDPE density: 0.898 g / cm 3 , MFR (190 ° C., 2.16 kg): 2.00 g / 10 min, melting point: 94 ° C.) (LDPE density: 0.923 g / cm 3 , MFR (190 ° C., 2.16 kg): 0.60 g / 10 min, melting point: 112 ° C.) 1% by weight, polyethylene elastomer (PE elastomer 1 (comonomer is 1 -Butene) Density 0.860 g / cm 3 , MFR (190 ° C., 2.16 kg): 0.50 g / 10 min, melting point 50 ° C.) 5 wt% were blended and kneaded to obtain The resin composition was evaluated for transparency at 23 ° C., heat-resistant rigidity at 80 ° C., and low-temperature impact resistance at −5 ° C. The density of physical properties and MFR were measured based on JIS K 7112, and the melting point was judged from the peak of DSC. Moreover, it is as follows when the mixing | blending of Example 1 is shown in a specific ratio. r-PP / LLDPE / LDPE /
[実施例2]
実施例1の配合においてPE系エラストマー1を密度とMFRが大きいPE系エラストマー2(コモノマーは1−ブテン 密度0.880g/cm3、MFR(190℃、2.16kg):1.20g/10min、融点66℃)に変更し、割合以外は実施例1と同じ条件にて樹脂組成物を作製し、評価を行った。実施例2の配合を具体的な割合で示すと以下のようになる。
r−PP/LLDPE/LDPE/PE系エラストマー2=84.6/9.4/1/5
[Example 2]
In the formulation of Example 1, PE-based
r-PP / LLDPE / LDPE / PE elastomer 2 = 84.6 / 9.4 / 1/5
[実施例3]
実施例1の配合においてPE系エラストマー1をコモノマーに使用する不飽和炭化水素の炭素数が増加したPE系エラストマー3(コモノマーは1−オクテン 密度0.863g/cm3、MFR(190℃、2.16kg):0.50g/10min、融点47℃)に変更し、割合以外は実施例1と同じ条件にて樹脂組成物を作製し、評価を行った。実施例3の配合を具体的な割合で示すと以下のようになる。
r−PP/LLDPE/LDPE/PE系エラストマー3=84.6/9.4/1/5
[Example 3]
PE-based elastomer 3 having an increased number of unsaturated hydrocarbons using PE-based
r-PP / LLDPE / LDPE / PE elastomer 3 = 84.6 / 9.4 / 1/5
[比較例1]
実施例1の配合からLDPEを除いた他は同じ条件にて樹脂組成物を作製し、評価を行った。比較例1の配合を具体的な割合で示すと以下のようになる。
r−PP/LLDPE/PE系エラストマー1=85.5/9.5/5
[Comparative Example 1]
A resin composition was prepared and evaluated under the same conditions except that LDPE was excluded from the formulation of Example 1. The composition of Comparative Example 1 is shown in a specific ratio as follows.
r-PP / LLDPE /
[比較例2]
実施例2の配合からLDPEを除いた他は同じ条件にて樹脂組成物を作製し、評価を行った。比較例2の配合を具体的な割合で示すと以下のようになる。
r−PP/LLDPE/PE系エラストマー1=85.5/9.5/5
[Comparative Example 2]
A resin composition was prepared and evaluated under the same conditions except that LDPE was excluded from the formulation of Example 2. The composition of Comparative Example 2 is shown in a specific ratio as follows.
r-PP / LLDPE /
[比較例3]
実施例3の配合からLDPEを除いた他は同じ条件にて樹脂組成物を作製し、評価を行った。比較例3の配合を具体的な割合で示すと以下のようになる。
r−PP/LLDPE/PE系エラストマー1=85.5/9.5/5
[Comparative Example 3]
A resin composition was prepared and evaluated under the same conditions except that LDPE was excluded from the formulation of Example 3. The composition of Comparative Example 3 is shown in a specific ratio as follows.
r-PP / LLDPE /
[比較例4]
実施例1の配合からLLDPEとLDPEを除いた他は同じ条件にて樹脂組成物を作製し、評価を行った。比較例4の配合を具体的な割合で示すと以下のようになる。
r−PP/PE系エラストマー1=85/15
[Comparative Example 4]
A resin composition was prepared and evaluated under the same conditions except that LLDPE and LDPE were excluded from the formulation of Example 1. The composition of Comparative Example 4 is shown in a specific ratio as follows.
r-PP /
[比較例5]
実施例1の配合からPE系エラストマー1とLDPEを除いた他は同じ条件にて樹脂組成物を作製し、評価を行った。比較例5の配合を具体的な割合で示すと以下のようになる。
r−PP/LLDPE=85/15
[Comparative Example 5]
A resin composition was prepared and evaluated under the same conditions except that the
r-PP / LLDPE = 85/15
容器の耐低温衝撃性を実際の落下試験をせずに材料の機械物性で推測する方法としてアイゾット衝撃強度がある。アイゾット衝撃強度については、JIS K 7110に基づき−5℃で測定し、結果を表1に示す。 There is an Izod impact strength as a method for estimating the low temperature impact resistance of a container from the mechanical properties of a material without performing an actual drop test. The Izod impact strength was measured at −5 ° C. based on JIS K 7110, and the results are shown in Table 1.
容器の耐熱剛性を推測するために、80℃における試験片の引張弾性率をJIS K 7161に基づき測定し、結果を表1に示す。 In order to estimate the heat-resistant rigidity of the container, the tensile modulus of the test piece at 80 ° C. was measured based on JIS K 7161, and the results are shown in Table 1.
可視光の透明性が高いと数値が大きくなる波長450nmの光線透過率を島津製作所株式会社 UV−2400PCにて測定した結果を表1に示す。 Table 1 shows the results of measuring the light transmittance at a wavelength of 450 nm, which increases the numerical value when the transparency of visible light is high, with UV-2400PC, Shimadzu Corporation.
上述した実施例1と比較例1は、ポリプロピレンと直鎖状ポリエチレンとポリエチレン系エラストマーの混合物にLDPEが配合されているものが実施例1で配合されていないのが比較例1である。実施例1は比較例1と比較するとアイゾット衝撃強度の引張弾性率の向上していることが分かる。 In Example 1 and Comparative Example 1 described above, Comparative Example 1 is that in which LDPE is blended in a mixture of polypropylene, linear polyethylene, and a polyethylene-based elastomer, but not blended in Example 1. It can be seen that Example 1 has improved tensile modulus of Izod impact strength as compared with Comparative Example 1.
このことは、LDPEがポリプロピレンと直鎖状ポリエチレンとポリエチレン系エラストマーの相溶性を向上させ、さらに結晶化率を向上させたことによると推測される。結晶化率とは、樹脂中に含まれる結晶の割合であり、結晶性樹脂には、耐熱剛性に優れる結晶部と耐熱剛性のない非晶部に分けられる。そして、混合樹脂の相溶性が向上することは、衝撃または応力を吸収するゴム成分を最も効果の発現するサブマイクロメーターオーダーに分散することにつながり低温衝撃性が向上する。さらに、結晶化率は分散が良くなることで樹脂が秩序よく配列し結晶化しやすくなるため大きくなる。耐熱剛性に優れる結晶成分が混合樹脂中に多く存在することになり耐熱剛性が向上することとなる。 This is presumably because LDPE improved the compatibility of polypropylene, linear polyethylene and polyethylene elastomer, and further improved the crystallization rate. The crystallization rate is a ratio of crystals contained in the resin, and the crystalline resin is divided into a crystal part having excellent heat resistance rigidity and an amorphous part having no heat resistance rigidity. The improvement in the compatibility of the mixed resin leads to the dispersion of the rubber component that absorbs impact or stress in the order of submicrometers where the most effective effect is achieved, and the low temperature impact property is improved. Furthermore, the crystallization rate increases because the dispersion is improved and the resin is arranged in an orderly manner and is easily crystallized. Many crystal components having excellent heat resistance rigidity are present in the mixed resin, and the heat resistance rigidity is improved.
このことは、実施例2と比較例2、実施例3と比較例3も同様に説明できる。 This can be explained in the same way in Example 2 and Comparative Example 2, and in Example 3 and Comparative Example 3.
実施例1〜3を比較するとPEエラストマーによって−5℃のアイゾッド衝撃強度と80℃の引張弾性率の改善傾向に差が見られた。最も効果があるPE系エラストマーは、アイゾット衝撃強度が4.67kJ/cm2から11.01kJ/cm2に上昇し、引張弾性率が126MPaから147MPaに上昇した実施例1のPE系エラストマーである。すなわち、密度が0.860g/cm3でコモノマーは1−ブテンのPE系エラストマーが最も改善効果が高いことが分かった。 When Examples 1 to 3 were compared, there was a difference in the improvement tendency of the izod impact strength of −5 ° C. and the tensile elastic modulus of 80 ° C. depending on the PE elastomer. The most effective PE-based elastomer is the PE-based elastomer of Example 1 having an Izod impact strength increased from 4.67 kJ / cm 2 to 11.01 kJ / cm 2 and a tensile elastic modulus increased from 126 MPa to 147 MPa. That is, it was found that a PE-based elastomer having a density of 0.860 g / cm 3 and 1-butene as the comonomer has the highest improvement effect.
また、屈折率の異なるポリプロピレンとポリエチレン系エラストマーをブレンドした配合では、透明性が低下する傾向になる。特に、比較例4のようにポリプロピレンに対してポリエチレン系エラストマーの相対量が多いとポリプロピレンはポリプロピレンで集合し、エラストマーはエラストマーで集合するため、分散が悪くなり極端に透明性が低下する。 Moreover, in the case of blending polypropylene and polyethylene elastomers having different refractive indexes, the transparency tends to decrease. In particular, as in Comparative Example 4, when the relative amount of polyethylene-based elastomer is large with respect to polypropylene, polypropylene aggregates with polypropylene and elastomer aggregates with elastomer, resulting in poor dispersion and extremely low transparency.
さらに、比較例4はエラストマーの比率が実施例1〜3と比べて大きいため、耐低温衝撃性が改善するものの、耐熱剛性が急激に悪化する。 Furthermore, since the ratio of the elastomer of Comparative Example 4 is larger than that of Examples 1 to 3, the low temperature impact resistance is improved, but the heat resistant rigidity is rapidly deteriorated.
比較例5では、実施例1〜3と比較してアイゾット衝撃強度が低く、直鎖状ポリエチレンを大量に入れても改善効果は小さいことがわかる。 In Comparative Example 5, it can be seen that the Izod impact strength is low as compared with Examples 1 to 3, and the improvement effect is small even when a large amount of linear polyethylene is added.
以上により、ポリプロピレンと、直鎖状低密度ポリエチレン、低密度ポリエチレン、ポリエチレン系エラストマーをブレンドした材料構成は、ポリプロピレンと、ポリエチレン系エラストマー、直鎖状低密度ポリエチレンをブレンドした材料構成と比較して−5℃のアイゾット衝撃値、80℃における剛性が向上することが分かる。このことは、低温耐衝撃性及び耐熱剛性に優れた透明性の高い容器を提供することができる。 As described above, the material composition blended with polypropylene, linear low density polyethylene, low density polyethylene, and polyethylene elastomer is compared with the material composition blended with polypropylene, polyethylene elastomer, and linear low density polyethylene. It can be seen that the Izod impact value at 5 ° C. and the rigidity at 80 ° C. are improved. This can provide a highly transparent container excellent in low-temperature impact resistance and heat-resistant rigidity.
最適な材料構成としては、ポリプロピレンが70%〜89%、ポリエチレン系エラストマー3%〜10%、直鎖状低密度ポリエチレン7%〜15%と、低密度ポリエチレン1%〜5%の割合でブレンドされた構成である。 The optimum material composition is 70% to 89% polypropylene, 3% to 10% polyethylene elastomer, 7% to 15% linear low density polyethylene, and 1% to 5% low density polyethylene. It is a configuration.
1 多層プラスチック容器
2 外層(混合層)
3 接着層
4 ガスバリア層
5 中間層
6 内層(混合層)
1 Multilayer plastic container 2 Outer layer (mixed layer)
3 Adhesive layer 4 Gas barrier layer 5 Intermediate layer 6 Inner layer (mixed layer)
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JP2017013809A (en) * | 2015-06-30 | 2017-01-19 | 三笠産業株式会社 | Multilayer container |
JP2017036069A (en) * | 2015-08-10 | 2017-02-16 | 大日本印刷株式会社 | Composite container, composite preform, manufacturing method of composite container, and plastic member |
WO2019044678A1 (en) * | 2017-08-31 | 2019-03-07 | キョーラク株式会社 | Delamination container |
JP7485943B2 (en) | 2020-08-31 | 2024-05-17 | キョーラク株式会社 | Plastic containers |
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JPS6198756A (en) * | 1984-10-20 | 1986-05-17 | Mitsui Petrochem Ind Ltd | Polypropylene composition having improved low-temperature impact resistance |
JPH09262948A (en) * | 1996-03-28 | 1997-10-07 | Mitsui Petrochem Ind Ltd | Resin laminate and its application |
JP2011025637A (en) * | 2009-07-29 | 2011-02-10 | Dic Corp | Co-extruded multi-layer film and packaging material comprising this film |
JP2012148811A (en) * | 2011-01-20 | 2012-08-09 | Kyoraku Co Ltd | Plastic container |
JP2012148810A (en) * | 2011-01-20 | 2012-08-09 | Kyoraku Co Ltd | Plastic container |
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JPS6198756A (en) * | 1984-10-20 | 1986-05-17 | Mitsui Petrochem Ind Ltd | Polypropylene composition having improved low-temperature impact resistance |
JPH09262948A (en) * | 1996-03-28 | 1997-10-07 | Mitsui Petrochem Ind Ltd | Resin laminate and its application |
JP2011025637A (en) * | 2009-07-29 | 2011-02-10 | Dic Corp | Co-extruded multi-layer film and packaging material comprising this film |
JP2012148811A (en) * | 2011-01-20 | 2012-08-09 | Kyoraku Co Ltd | Plastic container |
JP2012148810A (en) * | 2011-01-20 | 2012-08-09 | Kyoraku Co Ltd | Plastic container |
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JP2017013809A (en) * | 2015-06-30 | 2017-01-19 | 三笠産業株式会社 | Multilayer container |
JP2017036069A (en) * | 2015-08-10 | 2017-02-16 | 大日本印刷株式会社 | Composite container, composite preform, manufacturing method of composite container, and plastic member |
WO2019044678A1 (en) * | 2017-08-31 | 2019-03-07 | キョーラク株式会社 | Delamination container |
JP2019043604A (en) * | 2017-08-31 | 2019-03-22 | キョーラク株式会社 | Laminated release container |
JP7485943B2 (en) | 2020-08-31 | 2024-05-17 | キョーラク株式会社 | Plastic containers |
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