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JP4446474B2 - Laminated plastic products - Google Patents
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JP4446474B2 - Laminated plastic products - Google Patents

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JP4446474B2
JP4446474B2 JP2004277491A JP2004277491A JP4446474B2 JP 4446474 B2 JP4446474 B2 JP 4446474B2 JP 2004277491 A JP2004277491 A JP 2004277491A JP 2004277491 A JP2004277491 A JP 2004277491A JP 4446474 B2 JP4446474 B2 JP 4446474B2
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和幸 畠山
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Heiwa Kagaku Industry Co Ltd
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Description

本発明は、積層プラスチック製品に関し、特に、耐透水性、耐通気性、耐衝撃性、耐薬品性、成形性に優れ、かつ自然環境において容易に生分解され、燃焼時の発熱量が低く、環境負荷が小さい積層プラスチック製品に関する。   The present invention relates to laminated plastic products, and in particular, has excellent water permeability, breath resistance, impact resistance, chemical resistance, moldability, is easily biodegraded in a natural environment, and has a low calorific value during combustion. The present invention relates to laminated plastic products with low environmental impact.

使用済みの汎用樹脂が環境に重大な悪影響を及ぼすことから、これらの汎用樹脂に代わるものとして各種の生分解性樹脂製品が提案されている。しかし、これらの生分解性樹脂は、環境において自然に生分解されるという性質を有するものの、汎用樹脂と比較して耐透水性、耐通気性、耐衝撃性、耐薬品性等に劣るものが多く、化粧品、薬品、食品等の液体や粉体の容器として使用すると、収容物が空気や水分によって経時変化したり、容器自体が劣化してしまう等の問題があった。   Since used general-purpose resins have a serious adverse effect on the environment, various biodegradable resin products have been proposed as alternatives to these general-purpose resins. However, although these biodegradable resins have the property of being naturally biodegradable in the environment, they are inferior in water permeability, breath resistance, impact resistance, chemical resistance, etc. compared to general-purpose resins. In many cases, when used as a container for liquids or powders of cosmetics, medicines, foods, etc., there is a problem that the contents change with time due to air or moisture, or the container itself deteriorates.

この問題を解消するために、内層と外層を有する積層プラスチック製品において、外層の構成成分の50質量%以上が生分解性樹脂であり、内層がポリオレフィン樹脂であることを特徴とする生分解性プラスチック製品が提案されている(特許文献1参照)。しかし、内層として使用するポリオレフィン樹脂自体は生分解性ではないため、自然環境において完全には生分解されないという問題があることに加え、これらのポリオレフィン樹脂は燃焼時の発熱量が大きく、焼却炉を損傷しやすいという問題もあった。   In order to solve this problem, in a laminated plastic product having an inner layer and an outer layer, the biodegradable plastic is characterized in that 50% by mass or more of the constituent components of the outer layer is a biodegradable resin and the inner layer is a polyolefin resin. A product has been proposed (see Patent Document 1). However, since the polyolefin resin itself used as the inner layer is not biodegradable, there is a problem that it is not completely biodegradable in the natural environment. In addition, these polyolefin resins generate a large amount of heat during combustion. There was also a problem of being easily damaged.

また、環境において自然に生分解されるという性質を有し、かつ、汎用樹脂と比較して同等の耐透水性、耐通気性、耐衝撃性、耐薬品性等を有する樹脂として、テレフタル酸、エチレングリコール、ジエチレングリコール、5−スルホイソフタル酸を共重合したポリエステルが提案されている(特許文献2参照)。しかし、このポリエステルは成形性が悪いという問題があった。   In addition, as a resin having the property of being naturally biodegradable in the environment and having equivalent water permeability, breath resistance, impact resistance, chemical resistance, etc. compared to general-purpose resins, terephthalic acid, A polyester obtained by copolymerizing ethylene glycol, diethylene glycol, and 5-sulfoisophthalic acid has been proposed (see Patent Document 2). However, this polyester has a problem of poor moldability.

特開2001−225430JP 2001-225430 A 特表平5−507109Special table flat 5-507109

従って、本発明の目的は、耐透水性、耐通気性、耐衝撃性、耐薬品性、成形性に優れ、かつ自然環境において生分解されやすく、燃焼時の発熱量が低く、環境負荷が小さい積層プラスチック製品、特に、化粧品、薬品、又は食品の容器を提供することである。   Accordingly, the object of the present invention is excellent in water permeability, breath resistance, impact resistance, chemical resistance, moldability, biodegradation in the natural environment, low calorific value at the time of combustion, and low environmental load. It is to provide laminated plastic products, in particular cosmetic, pharmaceutical or food containers.

本発明の上記課題は、少なくとも内層、中間層及び外層を有する積層プラスチック製品において、内層及び外層をポリオレフィン樹脂で構成し、中間層を生分解性樹脂で構成することにより達成される。
本発明は以下の積層プラスチック製品を提供するものである。
1.少なくとも内層、中間層及び外層を有する積層プラスチック製品において、内層及び外層がポリオレフィン樹脂を50質量%以上含み、中間層が生分解性樹脂を50質量%以上含む、積層プラスチック製品。
2.生分解性樹脂が、ポリヒドロキシブチレート/バリレート、ポリ−β−ヒドロキシ酪酸、ポリブチレンサクシネート、ポリブチレンサクシネート/アジペート、ポリエチレンサクシネート、ポリカプロラクトン、ポリ乳酸、ポリビニルアルコール、デンプン、変性デンプン、キトサン/セルロース/デンプン及びこれらの2種以上の混合物、又は下記の式Iの繰り返し構造単位からなるスルホン酸基含有ポリエステルである上記1記載の積層プラスチック製品。
式I −CO−R−CO−OGO−
式中、Rは約97−99.9モル%のパラフェニレン及び約0.1−3モル%のスルホネート基
The above-described object of the present invention is achieved by forming the inner layer and the outer layer with a polyolefin resin and the intermediate layer with a biodegradable resin in a laminated plastic product having at least an inner layer, an intermediate layer, and an outer layer.
The present invention provides the following laminated plastic products.
1. A laminated plastic product having at least an inner layer, an intermediate layer, and an outer layer, wherein the inner layer and the outer layer contain 50% by mass or more of a polyolefin resin, and the intermediate layer contains 50% by mass or more of a biodegradable resin.
2. Biodegradable resins are polyhydroxybutyrate / valerate, poly-β-hydroxybutyric acid, polybutylene succinate, polybutylene succinate / adipate, polyethylene succinate, polycaprolactone, polylactic acid, polyvinyl alcohol, starch, modified starch, 2. The laminated plastic product according to 1 above, which is a sulfonic acid group-containing polyester composed of chitosan / cellulose / starch and a mixture of two or more thereof, or a repeating structural unit of the following formula I:
Formula I —CO—R—CO—OGO—
Wherein R is about 97-99.9 mole percent paraphenylene and about 0.1-3 mole percent sulfonate groups.

Figure 0004446474
であり、式中Mはアルカリ金属又はアルカリ土類金属であり、
Gは約60−80モル%の−CH2−CH2−及び約20−40モル%の−(CH22−O−(CH22−である。
3.ポリオレフィン樹脂が、ポリエチレン又はポリプロピレン又はポリエチレン−プロピレンであり、生分解性樹脂がポリ乳酸である上記1又は2記載の積層プラスチック製品。
4.内層及び外層の合計の厚みに対する中間層の厚みが1〜9である上記1〜3のいずれか1項記載の積層プラスチック製品。
5.ポリオレフィン樹脂が、30質量%以下の生分解誘導促進剤を含有する上記1〜4のいずれか1項記載の積層プラスチック製品。
6.化粧品、薬品、又は食品の容器である、上記1〜5のいずれか1項記載の積層プラスチック製品。
Figure 0004446474
Where M is an alkali metal or alkaline earth metal,
G is about 60-80 mol% —CH 2 —CH 2 — and about 20-40 mol% — (CH 2 ) 2 —O— (CH 2 ) 2 —.
3. 3. The laminated plastic product according to 1 or 2 above, wherein the polyolefin resin is polyethylene, polypropylene, or polyethylene-propylene, and the biodegradable resin is polylactic acid.
4). 4. The laminated plastic product according to any one of 1 to 3, wherein the intermediate layer has a thickness of 1 to 9 with respect to the total thickness of the inner layer and the outer layer.
5). The laminated plastic product according to any one of 1 to 4 above, wherein the polyolefin resin contains a biodegradation induction accelerator of 30% by mass or less.
6). The laminated plastic product according to any one of 1 to 5 above, which is a container for cosmetics, medicines or foods.

本発明の積層プラスチック製品は、耐透水性、耐通気性、耐衝撃性、耐薬品性、成形性に優れ、かつ自然環境において容易に生分解され、燃焼時の発熱量が低く、環境負荷が小さい。   The laminated plastic product of the present invention is excellent in water permeability, breath resistance, impact resistance, chemical resistance and moldability, is easily biodegraded in the natural environment, has a low calorific value during combustion, and has an environmental load. small.

本発明は、少なくとも内層、中間層及び外層を有する積層プラスチック製品において、内層及び外層がポリオレフィン樹脂を50質量%以上、好ましくは80質量%以上、最も好ましくは100質量%含み、中間層が生分解性樹脂を50質量%以上、好ましくは80質量%以上、最も好ましくは100質量%含む、積層プラスチック製品である。   The present invention relates to a laminated plastic product having at least an inner layer, an intermediate layer, and an outer layer. The inner layer and the outer layer contain 50% by mass or more, preferably 80% by mass or more, and most preferably 100% by mass, and the intermediate layer is biodegradable. It is a laminated plastic product containing a functional resin in an amount of 50 mass% or more, preferably 80 mass% or more, and most preferably 100 mass%.

本発明に使用される生分解性樹脂としては、ポリヒドロキシブチレート/バリレート、ポリ−β−ヒドロキシ酪酸、ポリブチレンサクシネート、ポリブチレンサクシネート/アジペート、ポリエチレンサクシネート、ポリカプロラクトン、ポリ乳酸、ポリビニルアルコール、デンプン、変性デンプン、セルロースアセテート、キトサン/セルロース/デンプン及びこれらの2種以上の混合物、又は上記の式Iの繰り返し構造単位からなるスルホン酸基含有ポリエステル等が挙げられる。
具体的な市販品の例としては、テラマック(登録商標)(ポリ乳酸:ユニチカ)、ノボン(登録商標)(デンプン(合成):ノボン・ジャパン)、ビオノーレ(登録商標)(ポリブチレンサクシネート、ポリブチレンサクシネート/アジペート:昭和高分子)、レイシア(登録商標)(ポリ乳酸:三井化学)、ラクトロン(登録商標)(カネボウ製)、プラクセル(登録商標)(ダイセル化学製)等が挙げられる。また、上記式Iの繰り返し構造単位からなるスルホン酸基含有ポリエステルは、例えば、特表平5−507109号公報記載の方法により製造することができ、市販品としては、デュポン株式会社製の生分解性ポリエステル「バイオマックス」(登録商標)がある。特に好ましい生分解性樹脂はポリ乳酸である。
Examples of the biodegradable resin used in the present invention include polyhydroxybutyrate / valerate, poly-β-hydroxybutyric acid, polybutylene succinate, polybutylene succinate / adipate, polyethylene succinate, polycaprolactone, polylactic acid, polyvinyl Examples thereof include alcohols, starches, modified starches, cellulose acetates, chitosan / cellulose / starch and mixtures of two or more thereof, or sulfonic acid group-containing polyesters composed of repeating structural units of the above formula I.
Specific examples of commercially available products include Terramac (registered trademark) (polylactic acid: Unitika), Novon (registered trademark) (starch (synthetic): Novon Japan), Bionore (registered trademark) (polybutylene succinate, poly Examples include butylene succinate / adipate: Showa High Polymer, Lacia (registered trademark) (polylactic acid: Mitsui Chemicals), Lactron (registered trademark) (manufactured by Kanebo), Plaxel (registered trademark) (manufactured by Daicel Chemical Industries), and the like. Moreover, the sulfonic acid group-containing polyester comprising the repeating structural unit of the above formula I can be produced, for example, by the method described in JP-T-5-507109. Polyester "Biomax" (registered trademark). A particularly preferred biodegradable resin is polylactic acid.

本発明に使用されるポリオレフィン樹脂としては、例えば、ポリエチレン、ポリプロピレン、ポリエチレン−プロピレン、ポリ塩化ビニル等が挙げられる。特にポリエチレン、ポリプロピレン、ポリエチレン−プロピレンが好ましい。本発明のプラスチック製品の内層及び外層はこれらポリオレフィン樹脂のみで構成されていてもよいが、生分解誘導促進剤(例えば、デグラ・ノボン(登録商標)(ノボン・ジャパン))を30質量%以下、好ましくは20質量%以下含有しても良い。   Examples of the polyolefin resin used in the present invention include polyethylene, polypropylene, polyethylene-propylene, and polyvinyl chloride. In particular, polyethylene, polypropylene, and polyethylene-propylene are preferable. Although the inner layer and the outer layer of the plastic product of the present invention may be composed only of these polyolefin resins, a biodegradation induction accelerator (for example, Degra Novon (registered trademark) (Nobon Japan)) is 30% by mass or less, Preferably, it may be contained in an amount of 20% by mass or less.

本発明の積層プラスチック製品において、内層及び外層の合計の厚みに対する中間層の厚みは好ましくは1〜9、さらに好ましくは2〜8である。中間層の厚み比が上記範囲より薄いと耐透水性、耐通気性、耐衝撃性、耐薬品性、成形性は優れるが、生分解性が低くなり、燃焼時の発熱量が高く環境負荷が大きくなり好ましくない。また、中間層の厚み比が上記範囲より厚いと、生分解性が高く、燃焼時の発熱量が低くなり環境負荷は小さくなるが、耐透水性、耐通気性、耐衝撃性、耐薬品性、成形性が低下する。
内層及び外層の厚みの比は好ましくは1:5〜5:1、さらに好ましくは1:2〜2:1である。本発明の積層プラスチック製品の内層、中間層及び外層の合計の厚みは、特に制限はなく、一般的な化粧品、医薬品、食品等のプラスチック製容器の厚みとほぼ同様であり、好ましくは0.5〜5mm、さらに好ましくは0.7〜1.5mmである。
In the laminated plastic product of the present invention, the thickness of the intermediate layer with respect to the total thickness of the inner layer and the outer layer is preferably 1 to 9, more preferably 2 to 8. If the thickness ratio of the intermediate layer is less than the above range, the water permeability, breath resistance, impact resistance, chemical resistance, and moldability are excellent, but the biodegradability is low, the calorific value during combustion is high, and the environmental load is low. It becomes large and is not preferable. In addition, if the thickness ratio of the intermediate layer is thicker than the above range, the biodegradability is high, the calorific value at the time of combustion is low and the environmental load is small, but the water permeability, breath resistance, impact resistance, chemical resistance , The moldability is reduced.
The ratio of the thickness of the inner layer to the outer layer is preferably 1: 5 to 5: 1, more preferably 1: 2 to 2: 1. The total thickness of the inner layer, the intermediate layer, and the outer layer of the laminated plastic product of the present invention is not particularly limited, and is substantially the same as the thickness of a plastic container for general cosmetics, pharmaceuticals, foods, etc., preferably 0.5 -5 mm, more preferably 0.7-1.5 mm.

本発明において内層、外層、中間層それぞれ、複数層設けることもできる。その場合各層の厚みは同一でも異なっていても良い。
また本発明において、各層間には接着層を設けても良い。接着層としては、例えば、SF−730(三井化学)や、各層の成分の混合物(例えば、1:1の混合物)が挙げられる。
In the present invention, a plurality of inner layers, outer layers, and intermediate layers may be provided. In that case, the thickness of each layer may be the same or different.
In the present invention, an adhesive layer may be provided between each layer. As an adhesion layer, SF-730 (Mitsui Chemicals) and the mixture (for example, 1: 1 mixture) of the component of each layer are mentioned, for example.

本発明のプラスチック製品の用途として好ましいものは、化粧品、医薬品、食品等の容器である。
本発明のプラスチック製品は通常の成形方法、例えば、中空成形、ブロー成形等により成形できる。成形温度は通常、150〜180℃、好ましくは160〜170℃程度が適当である。
Preferable applications of the plastic product of the present invention are containers for cosmetics, pharmaceuticals, foods and the like.
The plastic product of the present invention can be molded by an ordinary molding method such as hollow molding, blow molding or the like. The molding temperature is usually 150 to 180 ° C, preferably about 160 to 170 ° C.

内層及び外層樹脂としてポリエチレン樹脂(日本ポリエチレン株式会社:KB148A)を、中間層樹脂としてテラマック(登録商標)(ポリ乳酸:ユニチカ)を使用し、有限会社鈴木鉄工製、多層中空成形機(TB−SW−7P)を用いて、160℃の成形温度で成形し、内層の厚み90μm、中間層の厚み470μm、外層の厚み250μm、寸法(直径58.5mm、高さ137mm、厚み810μm)の容器を作成した。この容器は、化粧品、医薬品、食品等の容器として使用可能である。
この容器の燃焼時の発熱量は、全体をポリエチレン樹脂(日本ポリエチレン株式会社:KB148A)で作成した容器のそれに対して約71%であった。
Polyethylene resin (Japan Polyethylene Corporation: KB148A) is used as the inner layer and outer layer resin, and Terramac (registered trademark) (polylactic acid: Unitika) is used as the intermediate layer resin. A multilayer hollow molding machine (TB-SW) manufactured by Suzuki Tekko Co., Ltd. -7P) to form a container having an inner layer thickness of 90 μm, an intermediate layer thickness of 470 μm, an outer layer thickness of 250 μm, and dimensions (diameter 58.5 mm, height 137 mm, thickness 810 μm). did. This container can be used as a container for cosmetics, pharmaceuticals, foods and the like.
The calorific value at the time of combustion of this container was about 71% with respect to that of a container made entirely of polyethylene resin (Japan Polyethylene Corporation: KB148A).

Claims (6)

少なくとも内層、中間層及び外層を有する多層中空成形プラスチック容器において、
内層及び外層がポリオレフィン樹脂を50質量%以上含み、中間層が生分解性樹脂を50質量%以上含み、
ポリオレフィン樹脂がポリエチレン又はポリプロピレン又はポリエチレン−プロピレンであり、生分解性樹脂がポリ乳酸であり、
内層及び外層の合計の厚みに対する中間層の厚みが1〜9であり、
内層、中間層及び外層の合計の厚みが、0.5〜5mmである、
多層中空成形プラスチック容器
In a multilayer hollow molded plastic container having at least an inner layer, an intermediate layer and an outer layer,
The inner layer and the outer layer contain 50% by mass or more of polyolefin resin, the intermediate layer contains 50% by mass or more of biodegradable resin ,
The polyolefin resin is polyethylene or polypropylene or polyethylene-propylene, the biodegradable resin is polylactic acid,
The thickness of the intermediate layer with respect to the total thickness of the inner layer and the outer layer is 1 to 9,
The total thickness of the inner layer, the intermediate layer, and the outer layer is 0.5 to 5 mm.
Multi-layer hollow molded plastic container .
内層及び外層がポリオレフィン樹脂を80質量%以上含み、中間層が生分解性樹脂を80質量%以上含む請求項1記載の多層中空成形プラスチック容器。The multilayer hollow molded plastic container according to claim 1, wherein the inner layer and the outer layer contain 80% by mass or more of polyolefin resin, and the intermediate layer contains 80% by mass or more of biodegradable resin. 内層及び外層がポリオレフィン樹脂を100質量%含み、中間層が生分解性樹脂を100質量%含む請求項1記載の多層中空成形プラスチック容器。The multilayer hollow molded plastic container according to claim 1, wherein the inner layer and the outer layer contain 100% by mass of a polyolefin resin, and the intermediate layer contains 100% by mass of a biodegradable resin. 内層及び外層の合計の厚みに対する中間層の厚みが2〜8である請求項1〜3のいずれか1項記載の多層中空成形プラスチック容器。The multilayer hollow molded plastic container according to any one of claims 1 to 3, wherein the thickness of the intermediate layer is 2 to 8 with respect to the total thickness of the inner layer and the outer layer. ポリオレフィン樹脂が、30質量%以下の生分解誘導促進剤を含有する請求項1又は4記載の多層中空成形プラスチック容器。 The multilayer hollow molded plastic container according to claim 1 or 4 , wherein the polyolefin resin contains a biodegradation induction accelerator of 30% by mass or less . 化粧品、薬品、又は食品の容器である、請求項1〜5のいずれか1項記載の多層中空成形プラスチック容器。 The multilayer hollow molded plastic container according to any one of claims 1 to 5, which is a container for cosmetics, medicines or foods .
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JP2008080546A (en) * 2006-09-26 2008-04-10 Dainippon Printing Co Ltd Double container
JP4390798B2 (en) * 2006-11-16 2009-12-24 ユニチカ株式会社 Adhesive and laminate made of it
JP5144921B2 (en) * 2006-11-29 2013-02-13 出光ユニテック株式会社 Biodegradable multilayer sheet
JP5069943B2 (en) * 2007-05-07 2012-11-07 ダイセルパックシステムズ株式会社 Laminated sheet for containers
JP5191776B2 (en) * 2008-03-31 2013-05-08 株式会社吉野工業所 Plastic container
JP5074362B2 (en) * 2008-11-27 2012-11-14 三菱樹脂株式会社 Packaging film
JP5074363B2 (en) * 2008-11-27 2012-11-14 三菱樹脂株式会社 Packaging film
JP2011000770A (en) * 2009-06-17 2011-01-06 Mitsubishi Plastics Inc Packaging film
MY160062A (en) * 2009-07-23 2017-02-15 Tristano Pty Ltd Multilayer film
EP3143073B1 (en) 2014-05-12 2019-02-27 The Procter and Gamble Company Microtextured films with improved tactile impression and/or reduced noise perception
JP2020044717A (en) * 2018-09-19 2020-03-26 株式会社平和化学工業所 Resin molded product and method for producing the same
JP2024120117A (en) * 2021-06-28 2024-09-04 一英 山口 Laminate

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