JP5191776B2 - Plastic container - Google Patents
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- JP5191776B2 JP5191776B2 JP2008094355A JP2008094355A JP5191776B2 JP 5191776 B2 JP5191776 B2 JP 5191776B2 JP 2008094355 A JP2008094355 A JP 2008094355A JP 2008094355 A JP2008094355 A JP 2008094355A JP 5191776 B2 JP5191776 B2 JP 5191776B2
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- 229920003023 plastic Polymers 0.000 title claims description 18
- 239000004033 plastic Substances 0.000 title claims description 18
- 229920005989 resin Polymers 0.000 claims description 66
- 239000011347 resin Substances 0.000 claims description 66
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 30
- 239000004626 polylactic acid Substances 0.000 claims description 30
- 239000002028 Biomass Substances 0.000 claims description 23
- 229920003002 synthetic resin Polymers 0.000 claims description 13
- 239000000057 synthetic resin Substances 0.000 claims description 13
- 229920005672 polyolefin resin Polymers 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 239000003607 modifier Substances 0.000 claims description 8
- 229920002472 Starch Polymers 0.000 claims description 6
- 229920003232 aliphatic polyester Polymers 0.000 claims description 6
- 239000008107 starch Substances 0.000 claims description 6
- 235000019698 starch Nutrition 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 5
- 229920000704 biodegradable plastic Polymers 0.000 claims description 4
- 238000007493 shaping process Methods 0.000 claims 1
- 239000010410 layer Substances 0.000 description 53
- 229920013716 polyethylene resin Polymers 0.000 description 26
- 239000004698 Polyethylene Substances 0.000 description 24
- 239000004743 Polypropylene Substances 0.000 description 20
- 239000012790 adhesive layer Substances 0.000 description 12
- 230000004888 barrier function Effects 0.000 description 9
- 229920000139 polyethylene terephthalate Polymers 0.000 description 7
- 239000005020 polyethylene terephthalate Substances 0.000 description 7
- -1 polypropylene Polymers 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 239000004840 adhesive resin Substances 0.000 description 5
- 229920006223 adhesive resin Polymers 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000000071 blow moulding Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000004629 polybutylene adipate terephthalate Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 229920005839 ecoflex® Polymers 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 239000004959 Rilsan Substances 0.000 description 1
- 229920013627 Sorona Polymers 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- UVCJGUGAGLDPAA-UHFFFAOYSA-N ensulizole Chemical compound N1C2=CC(S(=O)(=O)O)=CC=C2N=C1C1=CC=CC=C1 UVCJGUGAGLDPAA-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920009537 polybutylene succinate adipate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
Landscapes
- Containers Having Bodies Formed In One Piece (AREA)
- Laminated Bodies (AREA)
Description
本発明は、バイオマスプラスチックを使用した合成樹脂製容器に関するものであり、耐内容物保存性・容器物性の劣化を極力抑制し、かつ、ＣＯ２の排出量の削減を図ろうとするものである。 The present invention relates to a synthetic resin container using biomass plastics, and intends to suppress deterioration of the content resistance storage stability and container physical properties as much as possible and to reduce CO 2 emissions.
食料品、飲料及び医薬品用容器に適用されているペットボトル等の合成樹脂製の容器は、その製造及び廃棄に際しては多大なエネルギーが消費されており、ＣＯ２排出量にも多大な影響を与えていることから、近年ではＣＯ２ 排出量の削減を図るのに有利な植物（植物はカーボンニュートラルの性質をもつことから、焼却時のＣＯ２排出量をカウントしない、及び／又は自然環境に存在するバクテリア等によって崩壊、消滅させることができる（生分解性））を原料としたバイオマスプラスチックを適用した容器の開発が試みられている。 Synthetic resin containers such as plastic bottles, which are applied to food, beverage and pharmaceutical containers, consume a great deal of energy during their production and disposal, and have a significant impact on CO 2 emissions. Therefore, in recent years, plants that are advantageous for reducing CO 2 emissions (because plants have carbon neutral properties, they do not count CO 2 emissions during incineration and / or exist in the natural environment. Attempts have been made to develop containers using biomass plastics made from raw materials that can be disintegrated and extinguished by bacteria (such as biodegradable).
かかるバイオマスプラスチックとしては、具体的にポリ乳酸（でんぷんの乳酸発酵物）樹脂、でんぷん樹脂、ＰＨＡ樹脂あるいは脂肪族ポリエステル樹脂等が存在しているが、何れの樹脂も水分を透過しやすい特性を有しており、液体又は固体を内容物として充填する容器にあってはそのままの状態では使用することができない不具合があり、この点に関する先行技術としてバイオマスプラスチックを中間層としてその内側及び外側にポリプロピレン樹脂やポリエチレンテレフタレート等からなる内層、外層を配設した積層複合型容器が提案されている（例えば、特許文献１参照）。
しかしながら、この種の容器はとくに、内容物の保存性の観点、容器物性を維持するための層構成及び材料選定が不十分であり、かつ中間層に落下等の衝撃に対する十分な強度をもたせることが困難なことから、未だ実用化の域には達しているとはいえないのが現状であった。 However, this type of container, in particular, has an insufficient layer structure and material selection for maintaining the physical properties of the contents, and the intermediate layer should have sufficient strength against impacts such as dropping. However, the current situation is that it has not yet reached the practical level.
本発明の課題は、内容物保存性の観点、容器物性を維持するための層構成及び材料選定、とくに耐衝撃性が改善され、ＣＯ２排出量を削減するのに有利な合成樹脂製容器を提案するところにある。 The object of the present invention is to provide a container made of a synthetic resin, which is advantageous in terms of storage stability of the contents, layer structure and material selection for maintaining the physical properties of the container, particularly impact resistance is improved, and CO 2 emission is reduced. Proposed.
本発明は、上記従来の課題を解決するためになされたものであり、
内外層の間に中間層を備えた積層型の合成樹脂製容器であって、
前記内外層は、オレフィン系樹脂であり、
前記中間層はバイオナスプラスチックを主成分とする構成体からなり、
前記内外層の樹脂の使用量が全樹脂量の２０〜７５質量％、前記中間層の樹脂の使用量が全樹脂量の２５〜８０質量％であり、該中間層は、ポリ乳酸、でんぷん樹脂、ＰＨＡ樹脂、バイオマスを主成分とする脂肪族ポリエステル及びバイオマスを由来とする非生分解性プラスチックのうちの少なくとも１種からなるとともに、中間層を形成する全樹脂量の１５質量％以下の柔軟性樹脂である改質剤を含有する、ことを特徴とする合成樹脂製容器である。
The present invention has been made to solve the above conventional problems,
A laminated synthetic resin container having an intermediate layer between inner and outer layers,
The inner and outer layers are olefin resins,
The intermediate layer is composed of a composition mainly composed of Bionasu plastic,
The amount of resin used in the inner and outer layers is 20 to 75% by mass of the total amount of resin, the amount of resin used in the intermediate layer is 25 to 80% by mass of the total amount of resin, and the intermediate layer is composed of polylactic acid and starch resin. , PHA resin, aliphatic polyester mainly composed of biomass, and non-biodegradable plastic derived from biomass, and having a flexibility of 15% by mass or less of the total resin amount forming the intermediate layer It is a synthetic resin container characterized by containing a modifier which is a resin.
上記の構成になる合成樹脂製容器において、内外層は、水分及び水蒸気透過の少ないポリプロピレン樹脂やポリエチレン樹脂、環状オレフィン樹脂のオレフィン樹脂が適用される。又はポリエチレンテレフタレート等芳香族ポリエステル樹脂でも代用可能である。 In the synthetic resin container having the above-described configuration, the inner and outer layers are made of a polypropylene resin, a polyethylene resin, or an olefin resin such as a cyclic olefin resin that transmits little moisture and water vapor. Alternatively, an aromatic polyester resin such as polyethylene terephthalate can be substituted.
また、中間層には、改質剤として柔軟性樹脂が添加され、中間層となるバイオマスプラスチックとしては、ポリ乳酸、でんぷん樹脂、ＰＨＡ樹脂又はバイオマスを主成分とする脂肪族ポリエステル及び／又はバイオマスを由来とする非生分解性プラスチック（バイオマスを主成分とする脂肪ポリエステルと、バイオマスを由来とする非生分解性プラスチックは、それぞれ単独で個別に適用される場合と、同時に適用される場合の２通りを含む）のうちの少なくとも１種が適用される。中間層には容器の成形時に生成されたスクラップ材（内層、中間層、外層を形成する樹脂）を添加することができる。 In addition, a flexible resin is added to the intermediate layer as a modifier, and the biomass plastic as the intermediate layer includes polylactic acid, starch resin, PHA resin, or aliphatic polyester and / or biomass mainly composed of biomass. Non-biodegradable plastics (derived from fatty polyesters mainly composed of biomass and non-biodegradable plastics derived from biomass) At least one of them is applied. A scrap material (resin forming the inner layer, the intermediate layer, and the outer layer) generated at the time of molding the container can be added to the intermediate layer.
中間層に、該中間層を形成する全樹脂量に対して１５質量％を上限として柔軟性樹脂を含有させて複合化を図ることにより該中間層は柔軟性を有することになり落下等の衝撃が加えられても簡単に破損するとこはない。また、柔軟性樹脂の使用量を抑えることで、バリア性の低下抑制及びＣＯ２排出量の抑制も可能となる。 When the intermediate layer is combined with a flexible resin up to 15% by mass with respect to the total amount of resin forming the intermediate layer, the intermediate layer becomes flexible and impact such as dropping. Even if is added, it will not break easily. In addition, by suppressing the amount of the flexible resin used, it is possible to suppress a decrease in barrier properties and a CO 2 emission amount.
容器の成形時に発生するスクラップ材は中間層に添加することが可能であり、その場合、改質剤としてＰＢＡＴ（ポリブチレンアジペート・テレフタレート）及びオレフィン系エラストマーを使用することが望ましく、これにより原料歩留りを高めることができる。 The scrap material generated during the molding of the container can be added to the intermediate layer. In this case, it is desirable to use PBAT (polybutylene adipate terephthalate) and olefin-based elastomer as modifiers. Can be increased.
内層、外層は、とくに内外気の水分に対して安定的な性質を有するポリプロピレン樹脂（ＰＰ）、ポリエチレン樹脂（ＰＥ）及び環状オレフィン樹脂（ＣＯＣ又はＣＯＰ）を使用し、求められる水分あるいは水蒸気バリア性を考慮してその使用量は容器を構成する全樹脂量の２０〜７５質量％とする。 The inner and outer layers use polypropylene resin (PP), polyethylene resin (PE), and cyclic olefin resin (COC or COP), which have properties that are particularly stable against moisture in the inside and outside air. The amount used is set to 20 to 75% by mass of the total resin amount constituting the container.
バイオマスプラスチックの使用量はＣＯ２の削減効果を発揮させる観点から全樹脂量の２５〜８０質量％とする。 The amount of the biomass plastic used is 25 to 80% by mass of the total resin amount from the viewpoint of exhibiting the CO 2 reduction effect.
バイオマスプラスチックに添加できる改質剤（柔軟性樹脂）としてはＰＢＡＴ（ＢＡＳＦ製エコフレックス（商品名））、ＰＴＭＡＴ（ケミテック製ＥａｓｔｅｒＢｉｏ（商品名））、ＰＢＳ（昭和高分子製ビオノーレ（商品名）、三菱化学製ＧＳ Ｐｌａ（商品名））、ＰＢＳＡ（昭和高分子製ビオノーレ(商品名)）、ＰＣＬ（ダイセル化学製セルグリーン（商品名）、ダウケミカル日本製ＴｏｎｅＰｏｌｙｍｅｒ（商品名））、ＰＣＬＢＳ（ダイセル化学製セルグリーン（商品名））、乳酸成分と脂肪族ポリエステル成分との共重合体（ＰＬＡ樹脂用改質剤として使用、大日本インキ社製プラメート（商品名））その他各種エラストマー（オレフィン系、エステル系等）等が適用される。 As modifiers (flexible resins) that can be added to biomass plastics, PBAT (BASF Ecoflex (trade name)), PTMAT (Chemtech EsterBio (trade name)), PBS (Showa High Polymer Bionore (trade name), Mitsubishi Chemical GS Pla (trade name)), PBSA (Showa Polymer Bionore (trade name)), PCL (Daicel Chemical Cell Green (trade name), Dow Chemical Japan Tone Polymer (trade name)), PCLBS (Daicel) Chemical green (trade name)), copolymer of lactic acid component and aliphatic polyester component (used as a modifier for PLA resin, Puramate (trade name) manufactured by Dainippon Ink Co., Ltd.) and other various elastomers (olefin-based, Ester type etc. are applied.
本発明にしたがう容器を製造するには、内層、外層及び中間層を形成するための樹脂の所定量をそれぞれ共押出して試験管状になるプリフォームを形成し、該プリフォームに対して所定の条件のもとでブロー成形を行うか、プリフォームを成形することなしに直接ブロー成形を行うダイレクトブロー成形法が適用される。 In order to produce a container according to the present invention, a predetermined amount of resin for forming an inner layer, an outer layer and an intermediate layer is coextruded to form a preform that becomes a test tube, and a predetermined condition is applied to the preform. A direct blow molding method is used in which blow molding is performed under the above conditions, or direct blow molding is performed without molding a preform.
本発明に適用し得るバイオマスプラスチックとしては、ポリ乳酸、でんぷん樹脂、ＰＨＡ樹脂又は脂肪族ポリエステルの少なくとも１種を適用することが可能であり、その他、ひまし油を主原料としたナイロン１１（アルケマ製リルサン（商品名））、とうもろこしを主原料としたＰＴＴ（デュポン製ソロナ(商品名)）を用いることもできる。 As the biomass plastic that can be applied to the present invention, at least one of polylactic acid, starch resin, PHA resin, or aliphatic polyester can be applied, and, in addition, nylon 11 mainly made from castor oil (Rilsan made by Arkema) (Trade name)), PTT (Sorona (trade name) manufactured by DuPont) using corn as the main raw material can also be used.
内外層を形成する樹脂としては、ＰＰ樹脂やＰＥ樹脂あるいは環状オレフィン樹脂、又はポリエチレンテレフタレート（ＰＥＴ）樹脂が適用される。 As the resin forming the inner and outer layers, PP resin, PE resin, cyclic olefin resin, or polyethylene terephthalate (PET) resin is applied.
容器の層構成は、内層、中間層、外層の３層構造に限定されるものではなく、用途に応じて種々変更が可能であり、また、各層は接着層（ＡＤ）を介して相互に接合する。 The layer structure of the container is not limited to a three-layer structure of an inner layer, an intermediate layer, and an outer layer, and can be variously changed according to the application. Each layer is bonded to each other via an adhesive layer (AD). To do.
実施例１
バイオマスプラスチックとしてＰＬＡ樹脂を使用した表１に示す３層構造になる容器（ボトル質量２０ｇ）を作製（成形条件：密度０．９５８のＨＤＰＥを内外層に使用し、中間層としてバイオマスプラスチック（ポリ乳酸（ＮａｔｕｒｅＷｏｒｋｓ社製））と中間層使用樹脂量に対して１５質量％のＢＡＳＦ製エコフレックスを添加して使用し、接着層は三井化学製アドマーＳＦ６００（以下、ＡＤと表記する）を使用し、ボトル質量２０ｇ中の５０質量％のポリ乳酸を配する層厚比にて試作した容器）してＰＰ樹脂単体、ＰＥ樹脂単体で作製した容器と比較しＣＯ２排出量の削減率(％)がどの程度にあるかについての調査を行った。その結果を表１に併せて示す。なお、表１〜４中オレフィン類とは、一般的なホモ・ブロック・ランダムＰＰ及びＰＰ系接着樹脂等のＰＰ系樹脂、一般的なＨＤＰＥ・Ｌ-ＬＤＰ及びＰＥ系接着剤等ＰＥ系樹脂を含むものとする。このうち、ＰＰ系接着樹脂やＰＥ系接着樹脂には、改質剤（柔軟性樹脂）として寄与する材料が存在する。
Example 1
A container (bottle mass 20 g) having a three-layer structure shown in Table 1 using PLA resin as a biomass plastic is produced (molding condition: HDPE having a density of 0.958 is used for inner and outer layers, and biomass plastic (polylactic acid is used as an intermediate layer) (Manufactured by NatureWorks)) and 15% by mass of BASF Ecoflex with respect to the amount of resin used in the intermediate layer, and an adhesive layer using Mitsui Chemicals Admer SF600 (hereinafter referred to as AD), CO 2 emission reduction rate (%) compared to a container made of PP resin alone and PE resin alone by making a prototype with a layer thickness ratio of 50% polylactic acid in 20 g of bottle mass We investigated the extent to which it was. The results are also shown in Table 1. In Tables 1 to 4, the olefins include PP resins such as general homo-block random PP and PP adhesive resins, and PE resins such as general HDPE / L-LDP and PE adhesives. Shall be included. Among these, PP-based adhesive resins and PE-based adhesive resins include materials that contribute as modifiers (flexible resins).
表１より明らかなように本発明にしたがう容器は通常のＰＰボトルやＰＥＴボトルに比較してＣＯ２の排出量が格段に軽減されることが確認された。なお、表中、環境配慮判定はＣＯ２のみの排出削減率である。合否判定としては、京都議定書目標（日本はＣＯ２とそれに換算した他５種の温室効果ガスの排出量を１９９０年に較べ６％削減することが定められている）を参考に、２００６年度実質削減率−１２％を基準として設定した。 As is apparent from Table 1, it was confirmed that the container according to the present invention significantly reduces the CO 2 emission compared to ordinary PP bottles and PET bottles. In the table, the environmental consideration judgment is the emission reduction rate of only CO 2 . The acceptance judgment, referring to the Kyoto Protocol Target (Japan while it is determined that the 6% reduction compared to emissions of other five greenhouse gases in terms of it with CO 2 in 1990), 2006 substantially A reduction rate of -12% was set as a reference.
実施例２
バイオマスプラスチックとしてＰＬＡ樹脂を使用した表２に示す層構成なる（２種３層：ＰＥ／ＰＬＡ系／ＰＥ、ＰＰ／ＰＬＡ系／ＰＰ、３種４層：ＰＥ／ＰＬＡ系／ＡＤ／ＰＥ、３種５層：ＰＥ/ＡＤ/ＰＬＡ系/ＡＤ/ＰＥ，ＰＰ/ＡＤ/ＰＬＡ系/ＡＤ/ＰＰ）で作製された質量２０ｇのボトル状容器、ＰＥＴ樹脂単体で作製した容器（質量２０ｇ）、ＰＬＡ樹脂とＰＥ樹脂とをブレンドした単層の容器（質量２０ｇ）につき、経時保管後の外観形状の変化について調査した。その結果を表２に併せて示す。なお、外観良否判定は、各種恒温恒湿度室にて長期間保存した際の、外観変化の有無で判断したものである。なお、ＰＬＡ樹脂に改質剤が添加されている場合には、ＰＬＡ系として表記した。
Layered composition shown in Table 2 using PLA resin as biomass plastic (2 types, 3 layers: PE / PLA system / PE, PP / PLA system / PP, 3 types, 4 layers: PE / PLA system / AD / PE, 3 5 layers of seeds: PE / AD / PLA system / AD / PE, PP / AD / PLA system / AD / PP) 20 g mass bottle-shaped container, PET resin alone container (mass 20 g), PLA With respect to a single layer container (mass 20 g) in which a resin and a PE resin were blended, the change in the external shape after storage over time was investigated. The results are also shown in Table 2. The appearance quality determination is based on the presence or absence of changes in appearance when stored in various constant temperature and humidity chambers for a long period of time. In addition, when the modifier was added to PLA resin, it described as PLA type | system | group.
実施例３
バイオマスプラスチックとしてＰＬＡ樹脂を使用した表３に示す層構成（２種３層：ＰＥ／ＰＬＡ系／ＰＥ（ＰＬＡ５０質量％）、３種４層：ＰＥ／ＰＬＡ系／ＡＤ／ＰＥ（ＰＬＡ５０質量％、ＰＬＡ７５質量％）、３種５層：ＰＥ/ＡＤ/ＰＬＡ系/ＡＤ/ＰＥ（ＰＬＡ２５質量％、ＰＬＡ５０質量％））を作製した質量２０ｇの容器、ＰＥ樹脂単体で作製した容器（質量２０ｇ）、ＰＬＡ樹脂とＰＥ樹脂とをブレンドした単層の容器、ＰＥＴ樹脂単体で作製した容器につき、水蒸気バリア性について調査した。その結果を表３に併せて示す。バリア性の判定は市販のビタミン等の製剤を容器内に規定量（約５０ｇ）添加し、高温多湿下で６０日保管した際の製剤の変色の有無で判断したものである。なお、表３において４０℃-７５％ＲＨ、６０日保管後の数値、４０℃-９０％ＲＨ、６０日保管後の値は、変化量をｇ（グラム）で表示している。
Example 3
Layer configuration shown in Table 3 using PLA resin as biomass plastic (2 types, 3 layers: PE / PLA system / PE (PLA 50 mass%), 3 types, 4 layers: PE / PLA system / AD / PE (PLA 50 mass%, PLA 75% by mass), 3 types and 5 layers: PE / AD / PLA system / AD / PE (PLA 25% by mass, PLA 50% by mass)), a 20 g mass container, a PE resin simple substance (mass 20 g), The water vapor barrier property was investigated for a single layer container obtained by blending PLA resin and PE resin, and a container made of PET resin alone. The results are also shown in Table 3. The determination of the barrier property is based on the presence or absence of discoloration of the preparation when a prescribed amount (about 50 g) of a preparation such as a commercially available vitamin is added to the container and stored for 60 days under high temperature and high humidity. In Table 3, 40 ° C.-75% RH, a value after storage for 60 days, and a value after 40 ° C.-90% RH, storage for 60 days are expressed in g (grams).
実施例４
バイオマスプラスチックとしてＰＬＡ樹脂を使用した表４に示す層構成（３種５層）で作製された容量が２００ｍｌになる容器を作製し、ＰＰ樹脂単体で作製した容器（２００ｍｌ）につき、水分バリア性について調査した。その結果を表４に併せて示す。バリア性の判定は容器内に水を２００ｍｌ充填し４０°Ｃ、３０日保管した際の水分透過率が１％以内であるかどうかで合格、不合格として判断したものである。なお、この実施例は５層の層構成以上で接着性樹脂を配置した場合におけるバリア性についての調査結果である。
Example 4
Using a PLA resin as a biomass plastic, a container with a capacity of 200 ml produced with the layer structure shown in Table 4 (3 types and 5 layers) was prepared, and the moisture barrier property of a container (200 ml) produced with PP resin alone investigated. The results are also shown in Table 4. The barrier property was judged as acceptable or unacceptable depending on whether or not the moisture permeability when the container was filled with 200 ml of water and stored at 40 ° C. for 30 days was within 1%. In addition, this Example is an investigation result on the barrier property in the case where the adhesive resin is arranged in a layer structure of five layers or more.
実施例５
バイオマスプラスチックとしてＰＬＡ樹脂を使用した表５、６に示す層構成になる容量２００ｍｌ、１００ｍｌの容器をそれぞれ製作し、ＰＰ樹脂単体で作製した容器、ＰＥ樹脂単体で作製した容器につき、落下による衝撃を加えた場合における破損状況について調査した。その結果を表５、６に併せて示す。なお、落下による衝撃は５°Ｃで２４時間保管したのち高さ１００ｃｍより垂直方向にて落下させたときの破損の有無で判定した。表５中ＰＰ系樹脂とは一般的なホモ・ブロック・ランダムＰＰ及びＰＰ系接着樹脂を含むものであり、表６中ＰＥ系樹脂とは一般的なＨＤＰＥ・Ｌ-ＬＤＰＥ及びＰＥ系接着剤を含むものである。なお、この実施例は、バリア性低下を考慮し、実使用上問題のないレベルの柔軟性樹脂配合での落下試験結果を示したものである。
Example 5
200ml and 100ml containers with the layer structure shown in Tables 5 and 6 using PLA resin as biomass plastic were produced, and impacts due to dropping were applied to containers made of PP resin alone and containers made of PE resin alone. The damage situation in the case of adding was investigated. The results are also shown in Tables 5 and 6. The impact due to dropping was determined by the presence or absence of damage when stored in a vertical direction from a height of 100 cm after being stored at 5 ° C. for 24 hours. In Table 5, PP resin includes general homo-block random PP and PP adhesive resin. In Table 6, PE resin includes general HDPE / L-LDPE and PE adhesive. Is included. In addition, this example shows the drop test result with a flexible resin blend at a level that does not cause a problem in actual use in consideration of a decrease in barrier properties.
上記調査の結果、本発明にしたがう合成樹脂製の容器は、ポリオレフィン樹脂製容器と比較して、ＣＯ２排出量の削減が可能であり、長期間にわたり保管しても経時的な劣化が極めて小さく、低温落下衝撃については高さ１ｍからの落下においても損傷は認められなかった。そして、水分バリア性、水蒸気バリア性はオレフィン系樹脂ボトルに対して大きく低下することはなく、再生材を使用してもとくに容器の品質に影響がないことが確認された。 As a result of the above investigation, the container made of synthetic resin according to the present invention can reduce CO 2 emission compared with the container made of polyolefin resin, and the deterioration over time is extremely small even when stored for a long period of time. Regarding the low temperature drop impact, no damage was observed even when dropped from a height of 1 m. Further, it was confirmed that the moisture barrier property and the water vapor barrier property are not greatly lowered with respect to the olefin resin bottle, and even when the recycled material is used, the quality of the container is not particularly affected.
衝撃強度が改善され、ＣＯ２排出量の削減に有利な合成樹脂製容器が提供できる。 The impact strength is improved, and a synthetic resin container advantageous in reducing CO 2 emission can be provided.
Claims (4)
前記内外層は、オレフィン系樹脂であり、
前記中間層はバイオマスプラスチックを主成分とする構成体からなり、
前記内外層の樹脂の使用量が全樹脂量の２０〜７５質量％、前記中間層の樹脂の使用量が全樹脂量の２５〜８０質量％であり、該中間層は、ポリ乳酸、でんぷん樹脂、ＰＨＡ樹脂、バイオマスを主成分とする脂肪族ポリエステル及びバイオマスを由来とする非生分解性プラスチックのうちの少なくとも１種からなるとともに、中間層を形成する全樹脂量の１５質量％以下の柔軟性樹脂である改質剤を含有する、ことを特徴とする合成樹脂製容器。 A laminated synthetic resin container having an intermediate layer between the inner layer and the outer layer,
The inner and outer layers are olefin resins,
The intermediate layer is composed of a biomass plastic as a main component,
The amount of resin used in the inner and outer layers is 20 to 75% by mass of the total amount of resin, the amount of resin used in the intermediate layer is 25 to 80% by mass of the total amount of resin, and the intermediate layer is composed of polylactic acid and starch resin. , PHA resin, aliphatic polyester mainly composed of biomass, and non-biodegradable plastic derived from biomass, and having a flexibility of 15% by mass or less of the total resin amount forming the intermediate layer A synthetic resin container comprising a modifier which is a resin.
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| JP6260597B2 (en) * | 2015-09-24 | 2018-01-17 | 大日本印刷株式会社 | Laminate of polyester resin composition |
| JP6226245B2 (en) * | 2015-09-24 | 2017-11-08 | 大日本印刷株式会社 | Laminate of polyester resin composition |
| JP6226247B2 (en) * | 2015-09-24 | 2017-11-08 | 大日本印刷株式会社 | Laminate of polyester resin composition |
| JP6226246B2 (en) * | 2015-09-24 | 2017-11-08 | 大日本印刷株式会社 | Laminate of polyester resin composition |
| JP6226248B2 (en) * | 2015-09-24 | 2017-11-08 | 大日本印刷株式会社 | Laminate of polyester resin composition |
| JP6256503B2 (en) * | 2016-03-14 | 2018-01-10 | 大日本印刷株式会社 | Laminate of polyester resin composition |
| JP6256502B2 (en) * | 2016-03-14 | 2018-01-10 | 大日本印刷株式会社 | Laminate of polyester resin composition |
| JP6344669B2 (en) * | 2017-01-19 | 2018-06-20 | 大日本印刷株式会社 | Laminate of polyester resin composition |
| JP6547817B2 (en) * | 2017-12-06 | 2019-07-24 | 大日本印刷株式会社 | Laminate of polyester resin composition |
| JP6706436B2 (en) * | 2019-06-26 | 2020-06-10 | 大日本印刷株式会社 | Laminate of polyester resin composition |
| JP2019155927A (en) * | 2019-06-26 | 2019-09-19 | 大日本印刷株式会社 | Laminate of polyester resin composition |
| JP7300379B2 (en) | 2019-11-06 | 2023-06-29 | 大日本印刷株式会社 | Films and packaging bags using plant-derived polyethylene resin |
| JP2021142030A (en) * | 2020-03-11 | 2021-09-24 | 有限会社齋藤歯研工業所 | Base plate for artificial tooth temporary adhesion and artificial tooth temporary adhesion body |
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