JP6013553B1 - Resin composition and hollow molded body - Google Patents
Resin composition and hollow molded body Download PDFInfo
- Publication number
- JP6013553B1 JP6013553B1 JP2015093236A JP2015093236A JP6013553B1 JP 6013553 B1 JP6013553 B1 JP 6013553B1 JP 2015093236 A JP2015093236 A JP 2015093236A JP 2015093236 A JP2015093236 A JP 2015093236A JP 6013553 B1 JP6013553 B1 JP 6013553B1
- Authority
- JP
- Japan
- Prior art keywords
- weight
- nylon mxd6
- polyethylene terephthalate
- hollow molded
- resin composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Containers Having Bodies Formed In One Piece (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
【課題】酸素バリア性、生産性、及び内容物の視認性の何れも良好で、液体を収容するプラスチックボトル等に好適な樹脂組成物の提供を目的とする。【解決手段】ポリエチレンテレフタレートと、ナイロンＭＸＤ６と、エチレン鎖及び水素結合性の極性基を有する共重合体とからなり、前記ポリエチレンテレフタレートを９３〜９８重量％、前記ナイロンＭＸＤ６を７〜２重量％、前記共重合体の添加量を、前記ポリエチレンテレフタレートとナイロンＭＸＤ６の１００重量％に対して０．０３〜０．８重量％とすることにより、インジェクションブロー成形によるプラスチックボトルの成形に好適な樹脂組成物を構成した。【選択図】なしAn object of the present invention is to provide a resin composition that is excellent in oxygen barrier properties, productivity, and visibility of contents, and that is suitable for a plastic bottle or the like that contains a liquid. SOLUTION: It comprises polyethylene terephthalate, nylon MXD6, and a copolymer having an ethylene chain and a hydrogen-bonding polar group, the polyethylene terephthalate is 93 to 98% by weight, the nylon MXD6 is 7 to 2% by weight, Resin composition suitable for molding of plastic bottle by injection blow molding by adding 0.03 to 0.8% by weight of said copolymer with respect to 100% by weight of said polyethylene terephthalate and nylon MXD6 Configured. [Selection figure] None
Description
本発明は、酸素バリア性が良好であり、かつ中空成形体を成形した場合に内容物の視認性に優れる樹脂組成物と中空成形体に関する。 The present invention relates to a resin composition and a hollow molded article that have good oxygen barrier properties and that are excellent in the visibility of the contents when the hollow molded article is molded.
従来、固体や液体が収納される樹脂製の中空成形体には、酸素バリア性が求められている。また、中空成形体に収納する収納物によっては、内容物の良好な視認性が求められることがある。例えば、調味料や飲料水などが収納されるプラスチックボトルは、内容物の劣化防止（酸素バリア性）及び不純物有無の視認性（内容物視認性）が求められる。 Conventionally, a resin-made hollow molded body in which a solid or a liquid is stored is required to have an oxygen barrier property. Moreover, the good visibility of the content may be calculated | required depending on the stored item accommodated in a hollow molded object. For example, plastic bottles that contain seasonings, drinking water, and the like are required to prevent deterioration of contents (oxygen barrier properties) and visibility of impurities (content visibility).
樹脂製の中空成形体として、ポリエチレンテレフタレート（ＰＥＴ）／ナイロンＭＸＤ６／ポリエチレンテレフタレートの三層構造、あるいはポリエチレンテレフタレート（ＰＥＴ）／ナイロンＭＸＤ６／ポリエチレンテレフタレート／ナイロンＭＸＤ６／ポリエチレンテレフタレートの五層構造のもの（特許文献１）や、内壁面に硬質炭素膜（ＤＬＣ）を形成したもの（特許文献２）などの複層タイプや、単層タイプ（特許文献３）が提案されている。 As a resin hollow molded body, a three-layer structure of polyethylene terephthalate (PET) / nylon MXD6 / polyethylene terephthalate or a five-layer structure of polyethylene terephthalate (PET) / nylon MXD6 / polyethylene terephthalate / nylon MXD6 / polyethylene terephthalate (patent) Document 1), a multilayer type such as a hard carbon film (DLC) formed on the inner wall surface (Patent Document 2), and a single layer type (Patent Document 3) have been proposed.
しかしながら、複層タイプは、酸素バリア性については高いが、複雑な工程を必要とする問題がある。また、単層タイプは、生産工程については簡易であるが、内容物の視認性に劣る問題がある。 However, the multi-layer type has a high oxygen barrier property but has a problem of requiring a complicated process. In addition, the single-layer type has a problem that the production process is simple, but the contents are inferior in visibility.
本発明は前記の点に鑑みなされたものであって、酸素バリア性、生産性、及び内容物の視認性の何れも良好な樹脂組成物と中空成形体の提供を目的とする。 This invention is made | formed in view of the said point, Comprising: It aims at provision of a resin composition and a hollow molded object with favorable all of oxygen barrier property, productivity, and the visibility of the content.
請求項１の発明は、ポリエチレンテレフタレートと、ナイロンＭＸＤ６と、エチレン−酢酸ビニル共重合体ケン化物とからなり、前記ポリエチレンテレフタレートが９３〜９８重量％、前記ナイロンＭＸＤ６が７〜２重量％、前記エチレン−酢酸ビニル共重合体ケン化物の添加量が、前記ポリエチレンテレフタレートとナイロンＭＸＤ６の１００重量％に対して０．０３〜０．０８重量％であることを特徴とする樹脂組成物に係る。 The invention of claim 1 comprises polyethylene terephthalate, nylon MXD6, and saponified ethylene-vinyl acetate copolymer , wherein the polyethylene terephthalate is 93 to 98% by weight, the nylon MXD6 is 7 to 2% by weight, and the ethylene -The addition amount of vinyl acetate copolymer saponified product is 0.03-0.08 weight% with respect to 100 weight% of the said polyethylene terephthalate and nylon MXD6, It concerns on the resin composition characterized by the above-mentioned.
請求項２の発明は、請求項１に記載の樹脂組成物をインジェクションブロー成形により成形して得た中空成形体を特徴とする。 The invention of claim 2 is characterized by a hollow molded body obtained by molding the resin composition of claim 1 by injection blow molding.
請求項３の発明は、請求項２における前記中空成形体は、延伸倍率が３〜７倍の部位における透過度（ＪＩＳ Ｋ ７３６１−１に準拠）が８０％以上であることを特徴とする。 The invention of claim 3 is characterized in that the hollow molded body of claim 2 has a transmittance (based on JIS K 7361-1) of 80% or more at a site where the draw ratio is 3 to 7 times.
請求項１の発明によれば、酸素バリア性、生産性（成形性）、内容物の視認性の何れも良好な樹脂組成物が得られる。
請求項２の発明によれば、請求項１の発明の樹脂組成物をインジェクションブロー成形した中空成形体は、酸素バリア性、及び内容物の視認性が良好でかつ生産性（成形性）が良好である。
請求項３の発明によれば、延伸倍率が３〜７倍の部位における透過度が８０％以上であるため、内容物の視認性が良好である。
According to the first aspect of the present invention, a resin composition having favorable oxygen barrier properties, productivity (moldability), and contents visibility can be obtained.
According to the invention of claim 2, the hollow molded body obtained by injection blow molding the resin composition of the invention of claim 1 has good oxygen barrier properties and contents visibility and good productivity (moldability). It is.
According to the invention of claim 3, the transparency of the contents is good because the transmittance at the site where the draw ratio is 3 to 7 times is 80% or more.
以下に本発明の樹脂組成物及び中空成形体について説明する。
本発明の樹脂組成物は、ポリエチレンテレフタレート（ＰＥＴ）と、ナイロンＭＸＤ６とエチレン−酢酸ビニル共重合体ケン化物とからなる。
ポリエチレンテレフタレートは、テレフタル酸とエチレングリコールとの重縮合によって製造することができる。
The resin composition and hollow molded body of the present invention will be described below.
The resin composition of the present invention comprises polyethylene terephthalate (PET), nylon MXD6, and saponified ethylene-vinyl acetate copolymer .
Polyethylene terephthalate can be produced by polycondensation of terephthalic acid and ethylene glycol.
ナイロンＭＸＤ６は、メタキシレンジアミン（ＭＸＤＡ）とアジピン酸との重縮合反応により得られる結晶性のポリアミドである。ナイロンＭＸＤ６はガスバリアー性に優れ、かつ強度及び弾性率が高く、低吸水性、低透湿性の特徴を有する。 Nylon MXD6 is a crystalline polyamide obtained by a polycondensation reaction of metaxylenediamine (MXDA) and adipic acid. Nylon MXD6 is excellent in gas barrier properties, has high strength and elastic modulus, and has characteristics of low water absorption and low moisture permeability.
ポリエチレンテレフタレートとナイロンＭＸＤ６の割合は、１００重量％中にポリエチレンテレフタレートを９３〜９８重量％、ナイロンＭＸＤ６を７〜２重量％が好ましい。なお、ポリエチレンテレフタレートの量を減らし過ぎる（ナイロンＭＸＤ６の量を増やし過ぎる）と、内容物の視認性が低下し、逆にポリエチレンテレフタレートの量を増やし過ぎる（ナイロンＭＸＤ６の量を減らし過ぎる）と、酸素バリア性が低下するようになる。 The ratio of polyethylene terephthalate to nylon MXD6 is preferably 93 to 98% by weight of polyethylene terephthalate and 7 to 2% by weight of nylon MXD6 in 100% by weight. If the amount of polyethylene terephthalate is reduced too much (the amount of nylon MXD6 is increased too much), the visibility of the contents will be lowered. Conversely, if the amount of polyethylene terephthalate is increased too much (the amount of nylon MXD6 is reduced too much), oxygen The barrier property is lowered.
エチレン−酢酸ビニル共重合体ケン化物の例として、例えば、東ソー社製の「メルセンＨ６４１０」、「メルセンＨ６０５１」、「メルセンＨ６８２０」等の「メルセンＨ」シリーズなどを挙げることができる。また、前記エチレン−酢酸ビニル共重合体ケン化物は、一種類に限られず、複数種類を併用してもよい。 Examples of the saponified ethylene-vinyl acetate copolymer include, for example, “Mersen H” series such as “Mersen H6410”, “Mersen H6051”, and “Mersen H6820” manufactured by Tosoh Corporation. Moreover, the ethylene-vinyl acetate copolymer saponified product is not limited to one type, and a plurality of types may be used in combination.
前記エチレン−酢酸ビニル共重合体ケン化物の添加量は、ポリエチレンテレフタレートとナイロンＭＸＤ６の合計１００重量％に対して０．０３〜０．０８重量％である。０．０３重量％よりも少ない場合には透過度（透明性）とヘイズ（曇り度）が悪化し内容物の視認性が低下するようになり、逆に０．０８重量％よりも多くなると、ヘイズ（曇り度）が上昇するようになる。 The addition amount of the saponified ethylene-vinyl acetate copolymer is 0.03 to 0.08% by weight based on 100% by weight of the total of polyethylene terephthalate and nylon MXD6. When the content is less than 0.03% by weight, the transparency (transparency) and haze (cloudiness) are deteriorated and the contents are less visible. On the contrary, when the content is more than 0.08% by weight, Haze (cloudiness) increases.
本発明の樹脂組成物は、ポリエチレンテレフタレートとナイロンＭＸＤ６とエチレン−酢酸ビニル共重合体ケン化物とを、溶融混練りして得られる。溶融混練りは、ペレット状のものを混合して溶融混練りする他に、マスターバッチとしたものを用いて溶融混練りしてもよい。 The resin composition of the present invention is obtained by melt-kneading polyethylene terephthalate, nylon MXD6, and saponified ethylene-vinyl acetate copolymer . The melt-kneading may be performed by melt-kneading using a master batch in addition to mixing and kneading pellets.
本発明の中空成形体は、前記樹脂組成物をインジェクションブロー成形して得られるボトル状のものである。ブロー成形には、押出ブロー成形とインジェクションブロー成形がある。
押出ブロー成形は、押出機から押し出した溶融状態のパリソンを金型内に配置し、パリソン内に空気を吹き込んで金型形状に膨らませ、冷却して金型内面形状の中空成形体を成形する方法である。
The hollow molded article of the present invention is a bottle-like product obtained by injection blow molding the resin composition. Blow molding includes extrusion blow molding and injection blow molding.
Extrusion blow molding is a method in which a melted parison extruded from an extruder is placed in a mold, air is blown into the parison to expand into a mold shape, and cooled to form a hollow molded body having an inner shape of the mold. It is.
インジェクションブロー成形（射出ブロー成形）は、射出成形によって形成した試験管状のプリフォームを金型にセットして、プリフォームに空気を吹き込んで中空成形体とする方法である。さらにインジェクションブロー成形の中でも延伸ブロー成形は、透明性及び強度の高い中空成形体が得られるため、好ましい成形方法である。 Injection blow molding (injection blow molding) is a method in which a test tubular preform formed by injection molding is set in a mold and air is blown into the preform to form a hollow molded body. Further, among the injection blow moldings, stretch blow molding is a preferable molding method because a hollow molded body having high transparency and strength can be obtained.
延伸ブロー成形には、ホットパリソン法とコールドパリソン法とがある。ホットパリソン法は、射出成形機でパリソンを成形し、そのパリソンが冷却する前に金型にセットし、空気を吹き込んで樹脂を延伸させ、中空成形体を成形する方法である。一方、コールドパリソン法は、射出成形により試験管状のパリソンを予め成形し、冷却したパリソンを延伸ブロー成形機の金型にセットして再加熱し、その状態で空気を吹き込んで樹脂を延伸させ、中空成形体を成形する方法である。 The stretch blow molding includes a hot parison method and a cold parison method. The hot parison method is a method in which a parison is molded by an injection molding machine, set in a mold before the parison is cooled, air is blown to stretch a resin, and a hollow molded body is molded. On the other hand, in the cold parison method, a test tube parison is molded in advance by injection molding, the cooled parison is set in a mold of a stretch blow molding machine and reheated, and air is blown in that state to stretch the resin. This is a method of forming a hollow molded body.
以下の成分を用いて表１の配合でインジェクションブロー成形し、実施例、参考例及び比較例の中空成形体を製造した。 Using the following components, injection blow molding was carried out with the composition shown in Table 1 to produce hollow molded bodies of Examples , Reference Examples and Comparative Examples .
・ポリエチレンテレフタレート（ＰＥＴ）：華潤有限公司製「ＣＲ８８１６」
・ナイロンＭＸＤ６：三菱ガス化学社製「Ｓ６００７」
・添加剤Ａ：酢酸ビニル含有率２８重量％のエチレン−酢酸ビニル共重合体の酢酸ビニル単位を１００％加水分解したエチレン−酢酸ビニル共重合体ケン化物、東ソー社製「メルセンＨ６０５１」
・添加剤Ｂ：エチレン−グリシジルメタクリレート−アクリル酸メチル共重合体、住友化学社製「（登録商標）ボンドファースト７Ｍ」
・添加剤Ｃ：グリシジルメタクリレート含有量１５重量％のエチレン−グリシジルメタクリレート共重合体（ＥＧＭＡ）とアクリロニトリルスチレン共重合体（ＡＳ）のグラフト共重合体（ＥＧＭＡ−ｇ−ＡＳ）、ＥＧＭＡ／ＡＳ（重量％比）＝７０／３０、日油社製「（登録商標）モディパーＡ４４００」
・ Polyethylene terephthalate (PET): “CR8816” manufactured by Huajun Co., Ltd.
・ Nylon MXD6: “S6007” manufactured by Mitsubishi Gas Chemical Company, Inc.
Additive A: Saponified ethylene-vinyl acetate copolymer obtained by hydrolyzing 100% of vinyl acetate unit of ethylene-vinyl acetate copolymer having a vinyl acetate content of 28% by weight, “Mersen H6051” manufactured by Tosoh Corporation
Additive B: ethylene-glycidyl methacrylate-methyl acrylate copolymer, “(registered trademark) Bond First 7M” manufactured by Sumitomo Chemical Co., Ltd.
Additive C: Graft copolymer (EGMA-g-AS), EGMA / AS (weight) of ethylene-glycidyl methacrylate copolymer (EGMA) and acrylonitrile styrene copolymer (AS) having a glycidyl methacrylate content of 15% by weight % Ratio) = 70/30, “(registered trademark) Modiper A4400” manufactured by NOF Corporation
インジェクションブロー成形は、インジェクションブロー成形機（日精エー・エス・ビー社製、型式：ＡＳＢ２５０ＥＸＨ）を用いて重量２７ｇ、全長１０５ｍｍの有底パリソン（プリフォーム）を成形した。この時の成形された有底パリソン（プリフォーム）の側面部の厚みは１．０ｍｍであった。
その後、その有底パリソン（プリフォーム）を８０〜１２０℃に調温して二軸延伸ブロー成形し、全長１６０ｍｍ、内容量３００ｍｌのボトル形状の中空成形体（容器）を成形した。
成形したボトル形状の中空成形体（容器）の側面部は、厚みが０．２ｍｍであり、成形時の延伸によって１／５の厚みとなり、延伸倍率が５倍であった。
In the injection blow molding, a bottomed parison (preform) having a weight of 27 g and a total length of 105 mm was molded using an injection blow molding machine (manufactured by Nissei ASB Co., Ltd., model: ASB250EXH). The thickness of the side part of the molded bottomed parison (preform) at this time was 1.0 mm.
Then, the bottomed parison (preform) was temperature-controlled at 80 to 120 ° C. and biaxially stretch blow molded to form a bottle-shaped hollow molded body (container) having a total length of 160 mm and an internal volume of 300 ml.
The side surface portion of the molded bottle-shaped hollow molded body (container) had a thickness of 0.2 mm, a thickness of 1/5 due to stretching during molding, and a stretching ratio of 5 times.
実施例１〜実施例３は、ＰＥＴとナイロンＭＸＤ６の割合を一定にして添加剤Ａの量のみを変化させた例、実施例４は実施例２と添加剤Ａの量を等しくしてＰＥＴの割合を実施例２よりも増大させた例である。また、参考例５と参考例６は、実施例２における添加剤Ａに代えて、添加剤Ｂ（参考例５）と添加剤Ｃ（参考例６）を使用した例である。 Examples 1 to 3 are examples in which the ratio of PET and nylon MXD6 is kept constant, and only the amount of additive A is changed. Example 4 is the same as that in Example 2 except that the amount of additive A is changed. This is an example in which the ratio is increased as compared with Example 2. Reference Example 5 and Reference Example 6 are examples using Additive B ( Reference Example 5) and Additive C ( Reference Example 6) instead of Additive A in Example 2.
比較例１〜比較例４は、添加剤Ａ〜Ｃの何れも添加せず、かつＰＥＴとナイロンＭＸＤ６の割合を変化させた例であり、比較例１はＰＥＴを１００重量％（ナイロンＭＸＤ６を０重量％）とした例、比較例２はＰＥＴを９９重量％、ナイロンＭＸＤ６を１重量％とした例、比較例３はＰＥＴを９５重量％、ナイロンＭＸＤ６を５重量％とした例、比較例４は、ＰＥＴを９０重量％、ナイロンＭＸＤ６を１０重量％とした例である。
比較例５と６は、ＰＥＴとナイロンＭＸＤ６の割合を実施例１〜３と同様の９５重量％と５重量％の一定にして、添加剤Ａの量を本発明の範囲外となる０．０２重量％（比較例５）と、０．１重量％（比較例６）にした比較例である。
Comparative Examples 1 to 4 are examples in which none of the additives A to C was added, and the ratio of PET and nylon MXD6 was changed. Comparative Example 1 was 100% by weight of PET (0% of nylon MXD6). Comparative Example 2 is an example in which PET is 99% by weight and nylon MXD6 is 1% by weight, Comparative Example 3 is an example in which PET is 95% by weight and nylon MXD6 is 5% by weight, Comparative Example 4 Is an example in which PET is 90% by weight and nylon MXD6 is 10% by weight.
In Comparative Examples 5 and 6, the ratio of PET and nylon MXD6 was kept constant at 95% by weight and 5% by weight as in Examples 1 to 3, and the amount of Additive A was outside the scope of the present invention. It is the comparative example made into weight% (comparative example 5) and 0.1 weight% (comparative example 6).
実施例、参考例及び比較例のボトル形状の中空成形体（容器）に対して、透過度（透明性）、ヘイズ（曇り度）、酸素透過度を以下の方法で測定した。
なお、内容物視認性については、透過度（透明性）及びヘイズ（曇り度）の両方の測定結果によって判断し、以下に示す透過度（透明性）及びヘイズ（曇り度）の評価が、何れも「〇」の場合に内容物視認性を良好「〇」とした。実施例、参考例及び比較例の測定結果及び評価は、配合と共に表１に示す。
Permeability (transparency), haze (cloudiness), and oxygen permeability of the bottle-shaped hollow molded bodies (containers) of Examples , Reference Examples and Comparative Examples were measured by the following methods.
The contents visibility is judged by the measurement results of both transparency (transparency) and haze (cloudiness), and the following evaluation of transparency (transparency) and haze (cloudiness) In the case of “◯”, the content visibility was set to “good”. The measurement results and evaluations of Examples , Reference Examples and Comparative Examples are shown in Table 1 together with the formulation.
・透過度（透明性）
有底パリソン（プリフォーム）の元厚が１．０ｍｍであったのが成形時の延伸によって０．２ｍｍとなった部位（延伸倍率５倍）において、紫外可視近赤外分光光度計（日本分光社製、名称：Ｖ−６５０）を用いてＪＩＳ Ｋ ７３６１−１に準拠してτ２（試験片を透過した全光束）とτ１（入射光の光束）を測定し、表１の下部に示した式（１）により［τｔ（全光透過率）％］を算出し、得られた［τｔ］を透過度（透明性）とした。評価は、透過度（％）が８０％以上を「〇」、８０％未満を「×」とした。
・ヘイズ（曇り度）
紫外可視近赤外分光硬度計（日本分光社製、名称：Ｖ−６５０）を用いてＪＩＳ Ｋ ７１３６に準拠してτ１（入射光の光束）、τ２（試験片を透過した全光束）、τ３（装置で拡散した光束）、τ４（装置及び試験片で拡散した光束）を測定し、表１の下部に示した式（２）により［ヘイズ（％）］を算出した。評価は、ヘイズ（曇り度）（％）が１５％以下を「〇」、１５％より大を「×」とした。
・酸素透過度
ＭＯＣＯＮ社製ＯＸ−ＴＲＡＮを用い、ＪＩＳ Ｋ７１２６−２に基づき、温度２３℃、容器内１００％ＲＨ／容器外５０％ＲＨの条件で酸素透過度を測定した。評価は、酸素透過度（ｃｍ３／ｄａｙ／ｂｏｔｔｌｅ／２．１３×１０４Ｐａ）が０．０２０以下を「〇」、０．０２０より大を「×」とした。
・ Transparency (transparency)
At the site where the original thickness of the bottomed parison (preform) was 1.0 mm but became 0.2 mm due to stretching at the time of molding (stretching ratio 5 times), an ultraviolet-visible near-infrared spectrophotometer (JASCO) Τ 2 (total light beam transmitted through the test piece) and τ 1 (light beam of incident light) were measured according to JIS K 7361-1 using the name of the company, name: V-650. [Τ t (total light transmittance)%] was calculated by the equation (1) shown, and the obtained [τ t ] was defined as the transmittance (transparency). In the evaluation, the transmittance (%) was 80% or more as “◯” and less than 80% as “x”.
・ Haze (cloudiness)
Using an ultraviolet-visible near-infrared spectroscopic hardness meter (manufactured by JASCO Corporation, name: V-650), τ 1 (light beam of incident light) and τ 2 (total light beam transmitted through the test piece) according to JIS K 7136 , Τ 3 (light beam diffused by the apparatus) and τ 4 (light beam diffused by the apparatus and the test piece) were measured, and [haze (%)] was calculated by the equation (2) shown in the lower part of Table 1. In the evaluation, a haze (cloudiness) (%) of 15% or less was “◯”, and a haze greater than 15% was “x”.
-Oxygen permeability Oxygen permeability was measured using MOX OX-TRAN based on JIS K7126-2 under conditions of a temperature of 23 ° C, 100% RH in the container / 50% RH outside the container. In the evaluation, oxygen permeability (cm 3 /day/bottom/2.13×10 4 Pa) was set to “◯” when 0.020 or less, and “×” when larger than 0.020.
実施例１〜４は、何れも透過度（透明性）、ヘイズ（曇り度）、酸素透過度の評価が「〇」であり、かつ、透過度（透明性）及びヘイズ（曇り度）が「〇」のため、内容物視認性の評価も良好［〇］である。 In each of Examples 1 to 4 , the evaluation of transparency (transparency), haze (cloudiness), and oxygen permeability is “◯”, and the transparency (transparency) and haze (cloudiness) are “ ○ ”, the content visibility evaluation is also good [◯].
一方、添加剤Ａ〜Ｃの何れも添加しない比較例１〜４のうち、ＰＥＴ１００％の比較例１と、ＰＥＴが９９重量％とナイロンＭＸＤ６が１重量％である比較例２は、透過度（透明性）とヘイズは「〇」であったが、酸素透過度が高い（酸素バリア性が低い）ものであった。また、ＰＥＴが９５重量％とナイロンＭＸＤ６が５重量％である比較例３と、ＰＥＴが９０重量％とナイロンＭＸＤ６が１０重量％である比較例４は、何れも酸素透過度が実施例１〜４と同程度であり、酸素バリア性が良好であったが、透過度（透明性）とヘイズが「×」、すなわち内容物視認性の評価が「×」であった。また、ＰＥＴが９５重量％とナイロンＭＸＤ６が５重量％である比較例５と比較例６のうち、添加剤Ａが０．０２重量％の比較例５については、透過度（透明性）とヘイズ（曇り度）が「×」、酸素透過度が「〇」であり、添加剤Ａが０．１重量％の比較例６については、透過度（透明性）が「〇」、ヘイズ（曇り度）が「×」、酸素透過度が「〇」であった。
On the other hand, among Comparative Examples 1 to 4 in which none of the additives A to C are added, Comparative Example 1 with 100% PET and Comparative Example 2 with 99% by weight of PET and 1% by weight of nylon MXD6 have a transmittance ( (Transparency) and haze were “◯”, but the oxygen permeability was high (oxygen barrier property was low). Further, in Comparative Example 3 in which PET is 95% by weight and nylon MXD6 is 5% by weight, and in Comparative Example 4 in which PET is 90% by weight and nylon MXD6 is 10% by weight, the oxygen permeability is in Examples 1 to 3. 4 and the oxygen barrier property was good, but the transparency (transparency) and haze were “x”, that is, the evaluation of the content visibility was “x”. Of Comparative Example 5 and Comparative Example 6 in which PET is 95% by weight and nylon MXD6 is 5% by weight, Comparative Example 5 in which Additive A is 0.02% by weight has transparency (transparency) and haze. (Comparative Example 6) in which the (cloudiness) is “×”, the oxygen permeability is “◯”, and the additive A is 0.1% by weight, the permeability (transparency) is “◯” and haze (cloudiness) ) Was “×” and the oxygen permeability was “◯”.
このように、本発明の樹脂組成物及び中空成形体は、酸素バリア性、生産性（成形性）、及び内容物の視認性の何れも良好である。 Thus, the resin composition and the hollow molded body of the present invention are all excellent in oxygen barrier properties, productivity (moldability), and contents visibility.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015093236A JP6013553B1 (en) | 2015-04-30 | 2015-04-30 | Resin composition and hollow molded body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015093236A JP6013553B1 (en) | 2015-04-30 | 2015-04-30 | Resin composition and hollow molded body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP6013553B1 true JP6013553B1 (en) | 2016-10-25 |
| JP2016210841A JP2016210841A (en) | 2016-12-15 |
Family
ID=57145218
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2015093236A Expired - Fee Related JP6013553B1 (en) | 2015-04-30 | 2015-04-30 | Resin composition and hollow molded body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6013553B1 (en) |
Citations (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6279258A (en) * | 1985-10-02 | 1987-04-11 | Teijin Ltd | Polyester bottle and production thereof |
| JPS62201963A (en) * | 1986-02-28 | 1987-09-05 | Toyobo Co Ltd | Polyester resin composition |
| JPS62257959A (en) * | 1986-05-01 | 1987-11-10 | Nissei Ee S B Kikai Kk | Biaxially orientated container |
| JPS62263250A (en) * | 1986-05-09 | 1987-11-16 | Teijin Ltd | Polyester resin composition |
| JPH03130125A (en) * | 1989-07-27 | 1991-06-03 | Ajinomoto Co Inc | Resin constituent body having gas barrier properties, manufacture thereof and resin composition used in manufacture therefor |
| JPH0425559A (en) * | 1990-05-22 | 1992-01-29 | Mitsubishi Kasei Corp | Resin composition |
| JPH055058A (en) * | 1991-06-27 | 1993-01-14 | Daicel Chem Ind Ltd | Film or sheet |
| JPH05214244A (en) * | 1992-01-31 | 1993-08-24 | Polyplastics Co | Molding resin composition |
| JP2003096282A (en) * | 2001-09-21 | 2003-04-03 | Toyobo Co Ltd | Polyester composition and molded article comprising the same |
| JP2003206346A (en) * | 2001-11-08 | 2003-07-22 | Toyobo Co Ltd | Method of manufacturing polyester composition |
| JP2004002804A (en) * | 2002-04-11 | 2004-01-08 | Toyobo Co Ltd | Polyester composition and molded product composed thereof |
| JP2004155994A (en) * | 2002-11-08 | 2004-06-03 | Toyobo Co Ltd | Polyester composition and molding composed of the same |
| JP2004323676A (en) * | 2003-04-24 | 2004-11-18 | Toyobo Co Ltd | Polyester, polyester molded item composed of the same and its manufacturing method |
| JP2006070101A (en) * | 2004-08-31 | 2006-03-16 | Mitsubishi Chemicals Corp | Polyester resin, resin composition, preform for stretch blow molding and hollow container |
| JP2006194335A (en) * | 2005-01-13 | 2006-07-27 | Kayaba Ind Co Ltd | Valve structure |
| JP2010235804A (en) * | 2009-03-31 | 2010-10-21 | Teijin Chem Ltd | Thermoplastic resin material for automotive fuel parts |
| JP2011037989A (en) * | 2009-08-11 | 2011-02-24 | Mitsubishi Gas Chemical Co Inc | Polyester container |
| JP2013185138A (en) * | 2012-03-09 | 2013-09-19 | Mitsubishi Gas Chemical Co Inc | Polyester-based resin composition |
| JP2015108134A (en) * | 2013-10-24 | 2015-06-11 | 三菱エンジニアリングプラスチックス株式会社 | Thermoplastic polyester resin composition |
-
2015
- 2015-04-30 JP JP2015093236A patent/JP6013553B1/en not_active Expired - Fee Related
Patent Citations (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6279258A (en) * | 1985-10-02 | 1987-04-11 | Teijin Ltd | Polyester bottle and production thereof |
| JPS62201963A (en) * | 1986-02-28 | 1987-09-05 | Toyobo Co Ltd | Polyester resin composition |
| JPS62257959A (en) * | 1986-05-01 | 1987-11-10 | Nissei Ee S B Kikai Kk | Biaxially orientated container |
| JPS62263250A (en) * | 1986-05-09 | 1987-11-16 | Teijin Ltd | Polyester resin composition |
| JPH03130125A (en) * | 1989-07-27 | 1991-06-03 | Ajinomoto Co Inc | Resin constituent body having gas barrier properties, manufacture thereof and resin composition used in manufacture therefor |
| JPH0425559A (en) * | 1990-05-22 | 1992-01-29 | Mitsubishi Kasei Corp | Resin composition |
| JPH055058A (en) * | 1991-06-27 | 1993-01-14 | Daicel Chem Ind Ltd | Film or sheet |
| JPH05214244A (en) * | 1992-01-31 | 1993-08-24 | Polyplastics Co | Molding resin composition |
| JP2003096282A (en) * | 2001-09-21 | 2003-04-03 | Toyobo Co Ltd | Polyester composition and molded article comprising the same |
| JP2003206346A (en) * | 2001-11-08 | 2003-07-22 | Toyobo Co Ltd | Method of manufacturing polyester composition |
| JP2004002804A (en) * | 2002-04-11 | 2004-01-08 | Toyobo Co Ltd | Polyester composition and molded product composed thereof |
| JP2004155994A (en) * | 2002-11-08 | 2004-06-03 | Toyobo Co Ltd | Polyester composition and molding composed of the same |
| JP2004323676A (en) * | 2003-04-24 | 2004-11-18 | Toyobo Co Ltd | Polyester, polyester molded item composed of the same and its manufacturing method |
| JP2006070101A (en) * | 2004-08-31 | 2006-03-16 | Mitsubishi Chemicals Corp | Polyester resin, resin composition, preform for stretch blow molding and hollow container |
| JP2006194335A (en) * | 2005-01-13 | 2006-07-27 | Kayaba Ind Co Ltd | Valve structure |
| JP2010235804A (en) * | 2009-03-31 | 2010-10-21 | Teijin Chem Ltd | Thermoplastic resin material for automotive fuel parts |
| JP2011037989A (en) * | 2009-08-11 | 2011-02-24 | Mitsubishi Gas Chemical Co Inc | Polyester container |
| JP2013185138A (en) * | 2012-03-09 | 2013-09-19 | Mitsubishi Gas Chemical Co Inc | Polyester-based resin composition |
| JP2015108134A (en) * | 2013-10-24 | 2015-06-11 | 三菱エンジニアリングプラスチックス株式会社 | Thermoplastic polyester resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2016210841A (en) | 2016-12-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7666486B2 (en) | Multi-layered biaxial stretch blow molded bottle and method for production thereof | |
| EP2910483B1 (en) | Plastic container having pearl-like appearance and preform for producing the same | |
| JP6787317B2 (en) | Multi-layer preform and multi-layer stretch blow molded container | |
| JPWO2007083598A1 (en) | Multilayer bottle | |
| KR101171585B1 (en) | Container made of synthetic resin having excellent barrier properties | |
| JP2006001108A (en) | Preform and blow-molded container obtained from preform | |
| JP5315599B2 (en) | Resin composition and multilayer structure | |
| KR20180073590A (en) | Medical multilayer container and method of manufacturing multilayer medical container | |
| JP4821353B2 (en) | Multilayer bottle | |
| KR20160103088A (en) | Multilayered stretch-blow-molded container and multilayered preform | |
| JP2015157470A (en) | Multilayer preform, and multilayer stretch blow molded container | |
| JP5673010B2 (en) | Multilayer bottle | |
| JPS58160344A (en) | Hollow polyester molding having excellent gas barrier properties | |
| KR20050067213A (en) | Preform, process for producing the same, and biaxially stretched container obtained from the preform | |
| JP6013553B1 (en) | Resin composition and hollow molded body | |
| JP2018126315A (en) | Multilayer container and multilayer body | |
| JP5563509B2 (en) | Multilayer structures and containers | |
| JP6305182B2 (en) | Multi-layer container | |
| JP4022091B2 (en) | Multi-layer blow molded container with excellent impact resistance | |
| JP2015157468A (en) | Multilayer stretch blow molded container | |
| EP4019249A1 (en) | Resin layered body | |
| JP2004168039A (en) | Preform, its manufacturing method, and container produced by biaxially stretching the preform | |
| JP6661914B2 (en) | Polyamide resin composition, molded article and method for producing molded article | |
| JP2017048283A (en) | Resin pellet and hollow molded body | |
| JP2017013809A (en) | Multilayer container |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20160727 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20160920 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20160921 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6013553 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |