JP2018154369A - Pet molding container and manufacturing method thereof - Google Patents
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- JP2018154369A JP2018154369A JP2017053222A JP2017053222A JP2018154369A JP 2018154369 A JP2018154369 A JP 2018154369A JP 2017053222 A JP2017053222 A JP 2017053222A JP 2017053222 A JP2017053222 A JP 2017053222A JP 2018154369 A JP2018154369 A JP 2018154369A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 238000000465 moulding Methods 0.000 title abstract description 25
- 239000002344 surface layer Substances 0.000 claims abstract description 68
- 239000010410 layer Substances 0.000 claims abstract description 45
- 238000002425 crystallisation Methods 0.000 claims abstract description 13
- 230000008025 crystallization Effects 0.000 claims abstract description 13
- 238000003856 thermoforming Methods 0.000 claims abstract description 4
- 239000003484 crystal nucleating agent Substances 0.000 claims description 27
- 230000035939 shock Effects 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 99
- 239000005020 polyethylene terephthalate Substances 0.000 description 99
- 229920008651 Crystalline Polyethylene terephthalate Polymers 0.000 description 18
- 239000000463 material Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 229920001225 polyester resin Polymers 0.000 description 7
- 239000004645 polyester resin Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- -1 polyethylene terephthalate Polymers 0.000 description 4
- 238000002156 mixing Methods 0.000 description 3
- 229920005672 polyolefin resin Polymers 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- 101150015738 Fev gene Proteins 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 102100037681 Protein FEV Human genes 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 235000013611 frozen food Nutrition 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920013716 polyethylene resin Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000015067 sauces Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Containers Having Bodies Formed In One Piece (AREA)
- Laminated Bodies (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、光沢度及び耐熱性に優れると共に、結晶性ポリエチレンテレフタレート（Ｃ−ＰＥＴ）成形容器と比べて耐寒衝撃性が向上したポリエチレンテレフタレート（ＰＥＴ）成形容器及びその製造方法に関する。 The present invention relates to a polyethylene terephthalate (PET) molded container having excellent glossiness and heat resistance, and having improved cold impact resistance compared to a crystalline polyethylene terephthalate (C-PET) molded container, and a method for producing the same.
ＰＥＴは、化学的及び物理的性質に優れ、飲料ボトル等の容器、フィルム、及びシート等に広く利用されている。近年、家庭用の電子レンジ及びオーブンが普及し、様々な半調理済みの冷凍食品が流通している。このような食品に使用される容器は、単に内容物を収容するだけでなく、広い温度範囲での使用に耐え得る耐熱性及び耐衝撃性が求められる。 PET has excellent chemical and physical properties and is widely used in containers such as beverage bottles, films, and sheets. In recent years, household microwave ovens and ovens have become widespread, and various semi-cooked frozen foods have been distributed. Containers used for such foods are required not only to contain the contents but also to have heat resistance and impact resistance that can withstand use in a wide temperature range.
従来、耐熱性に優れたＰＥＴ容器として、金型中で二次成形及び結晶化することにより得られるＣ−ＰＥＴ成形容器が実用化されている。ＰＥＴ成形容器の物性を改善するために、種々の技術が提案されている。例えば、特許文献１には、内外側に非晶性ＰＥＴ、中間層に結晶性ＰＥＴが配置され、各層が非晶状態である積層シートを、結晶性ＰＥＴの結晶化温度以下の温度で熱成形し、次いで、外側から結晶性ＰＥＴの結晶化温度に加熱することにより、中間層の結晶性ＰＥＴを熱結晶化させる耐熱ＰＥＴ容器の製造方法が記載されている。特許文献２には、固有粘度（ＩＶ値）が０．７０ｄｌ／ｇのポリエステル系樹脂と、ｎ−ヘキサン抽出成分が３重量％以下のポリオレフィン樹脂と、を含むポリエステル系樹脂シート及びその成形品が記載されている。 Conventionally, as a PET container excellent in heat resistance, a C-PET molded container obtained by secondary molding and crystallization in a mold has been put into practical use. Various techniques have been proposed to improve the physical properties of PET molded containers. For example, in Patent Document 1, amorphous PET is disposed on the inner and outer sides, crystalline PET is disposed on the intermediate layer, and a laminated sheet in which each layer is in an amorphous state is thermoformed at a temperature lower than the crystallization temperature of crystalline PET. Then, a method for producing a heat-resistant PET container is described in which the crystalline PET in the intermediate layer is thermally crystallized by heating from the outside to the crystallization temperature of crystalline PET. Patent Document 2 discloses a polyester resin sheet containing a polyester resin having an intrinsic viscosity (IV value) of 0.70 dl / g, and a polyolefin resin having an n-hexane extraction component of 3% by weight or less, and a molded product thereof. Have been described.
ＰＥＴ容器においても、上記のように、広い温度範囲での使用に耐え得る耐熱性及び耐衝撃性が求められる。しかし、Ｃ−ＰＥＴ成形容器は耐熱性に優れる反面、耐衝撃性に劣るという問題点がある。また、Ｃ−ＰＥＴ成形容器は成形の際、結晶化のために含まれているポリオレフィン系樹脂等の結晶核剤が、ロール又は金型に付着し、歩留りが悪いことが問題となっている。更に、通常、Ｃ−ＰＥＴはＡ−ＰＥＴ（本書面において「Ａ−ＰＥＴ」とは、一般的に結晶化していない状態であるが、結晶化温度以上で長時間加熱する等の方法により結晶化させることもできるＰＥＴを意味する。）と比べると、光沢度及び耐熱性に劣るという問題がある。 Also in the PET container, as described above, heat resistance and impact resistance that can withstand use in a wide temperature range are required. However, while the C-PET molded container is excellent in heat resistance, it has a problem that it is inferior in impact resistance. Further, the C-PET molded container has a problem in that the yield is poor because a crystal nucleating agent such as a polyolefin-based resin included for crystallization adheres to a roll or a mold during molding. Furthermore, C-PET is usually A-PET (in this document, “A-PET” is generally not crystallized, but is crystallized by a method such as heating for a long time above the crystallization temperature. Compared with PET, which can also be made to have a glossiness and heat resistance, there is a problem.
本発明は、光沢度及び耐熱性に優れると共に、Ｃ−ＰＥＴ成形容器と比べて耐衝撃性が向上したＰＥＴ成形容器及びその製造方法を提供することを目的とする。 An object of the present invention is to provide a PET molded container excellent in glossiness and heat resistance and having improved impact resistance as compared with a C-PET molded container, and a method for producing the same.
本発明のＰＥＴ成形容器は、Ｃ−ＰＥＴを含む中間層と、結晶核剤を含有しない非晶状態のＰＥＴで構成され、前記中間層の外側表面及び内側表面に積層された外側表面層及び内側表面層と、を有し、前記外側表面層及び内側表面層の厚みの合計が、容器全体の厚みの１６％以内であることを特徴とする。 The PET molded container of the present invention comprises an intermediate layer containing C-PET and an amorphous PET containing no crystal nucleating agent, and an outer surface layer and an inner layer laminated on the outer surface and the inner surface of the intermediate layer. And the total thickness of the outer surface layer and the inner surface layer is within 16% of the total thickness of the container.
本発明のＰＥＴ成形容器の製造方法は、結晶核剤及びＩＶ＝０．７以上の非晶状態のＰＥＴを含む中間層と、結晶核剤を含有しない非晶状態のＰＥＴで構成され、前記中間層の外側表面及び内側表面に積層された外側表面層及び内側表面層と、を有し、前記外側表面層及び内側表面層の厚みの合計が、シート全体の厚みの１６％以内である積層シートを、ＰＥＴの結晶化温度以上の温度で熱成形し、前記中間層の非晶状態のＰＥＴを結晶化することを特徴とする。 The method for producing a PET molded container of the present invention comprises a crystal nucleating agent and an intermediate layer containing an amorphous PET having an IV of 0.7 or more, and an amorphous PET containing no crystal nucleating agent, A laminated sheet having an outer surface layer and an inner surface layer laminated on the outer surface and the inner surface of the layer, wherein the total thickness of the outer surface layer and the inner surface layer is within 16% of the total thickness of the sheet Is thermoformed at a temperature equal to or higher than the crystallization temperature of PET to crystallize the amorphous PET in the intermediate layer.
本発明のＰＥＴ成形容器は、光沢度に優れ、Ｃ−ＰＥＴ成形容器と同等の耐熱性を有すると共に、全てＣ−ＰＥＴ層のみからなる成形容器と比べて耐寒衝撃性に優れている。よって、本発明のＰＥＴ成形容器は、広い温度範囲での使用に耐え得る耐熱性及び耐衝撃性を有する。本発明のＰＥＴ成形容器の製造方法では、成形時のロール汚れ又は金型汚れを低減することができる。よって、本発明の製造方法では、ＰＥＴ成形容器の製造における歩留りを改善することができる。 The PET molded container of the present invention is excellent in glossiness, has the same heat resistance as that of a C-PET molded container, and is excellent in cold shock resistance as compared with a molded container consisting entirely of a C-PET layer. Therefore, the PET molded container of the present invention has heat resistance and impact resistance that can withstand use in a wide temperature range. In the method for producing a PET molded container of the present invention, roll dirt or mold dirt at the time of molding can be reduced. Therefore, in the production method of the present invention, the yield in the production of the PET molded container can be improved.
本発明の実施の形態について以下説明する。本実施形態は本発明を実施する一例であって、本発明は本実施形態に限定されるものではない。 Embodiments of the present invention will be described below. This embodiment is an example for carrying out the present invention, and the present invention is not limited to this embodiment.
（１）ＰＥＴ成形容器
本実施形態に係るＰＥＴ成形容器（以下、「本容器」という。）は、結晶性ＰＥＴ（Ｃ−ＰＥＴ）を含む中間層と、結晶核剤を含有しない非晶状態のＰＥＴで構成され、前記中間層の外側表面及び内側表面に積層された外側表面層及び内側表面層と、を有し、前記外側表面層及び内側表面層の厚みの合計が、容器全体の厚みの１６％以内である。
(1) PET Molded Container A PET molded container (hereinafter referred to as “the present container”) according to this embodiment is an amorphous layer containing no crystalline nucleating agent and an intermediate layer containing crystalline PET (C-PET). An outer surface layer and an inner surface layer made of PET and laminated on the outer surface and the inner surface of the intermediate layer, and the total thickness of the outer surface layer and the inner surface layer is the total thickness of the container Within 16%.
前記中間層は、前記外側表面層及び内側表面層（以下、両者を総称して「表面層」という。）に間に位置し、Ｃ−ＰＥＴを含む層である。前記中間層は単層構造でもよく、結晶化の程度等が異なる多層構造でもよい。 The intermediate layer is located between the outer surface layer and the inner surface layer (hereinafter collectively referred to as “surface layer”) and is a layer containing C-PET. The intermediate layer may have a single layer structure or a multilayer structure with different degrees of crystallization.
前記Ｃ−ＰＥＴの結晶化度については特に限定はない。該結晶化度は通常、１０〜４０％である。前記Ｃ−ＰＥＴは通常、ＰＥＴ及び結晶核剤を含有する組成物を結晶化することにより形成される。前記結晶核剤は、ＰＥＴを結晶化することができる限り、その種類及び含有量に特に限定はない。前記結晶核剤として、例えば、ポリオレフィン（例えば、ポリエチレン）系樹脂等の有機結晶核剤、並びにタルク、カオリン、及びシリカ等の無機結晶核剤が挙げられる。前記結晶核剤として好ましくは、ポリオレフィン系樹脂を含有する結晶核剤であり、より好ましくは、ポリエチレン系樹脂を含有する結晶核剤である。前記結晶核剤の含有量は、前記中間層を形成するための、ＰＥＴ及び結晶核剤を含有する組成物全量中、０．５〜１０重量％、好ましくは１〜８重量％、更に好ましくは１〜６質量％である。 There is no particular limitation on the crystallinity of the C-PET. The crystallinity is usually 10 to 40%. The C-PET is usually formed by crystallizing a composition containing PET and a crystal nucleating agent. The type and content of the crystal nucleating agent are not particularly limited as long as PET can be crystallized. Examples of the crystal nucleating agent include organic crystal nucleating agents such as polyolefin (for example, polyethylene) resins, and inorganic crystal nucleating agents such as talc, kaolin, and silica. The crystal nucleating agent is preferably a crystal nucleating agent containing a polyolefin resin, and more preferably a crystal nucleating agent containing a polyethylene resin. The content of the crystal nucleating agent is 0.5 to 10% by weight, preferably 1 to 8% by weight, more preferably in the total amount of the composition containing PET and the crystal nucleating agent for forming the intermediate layer. 1 to 6% by mass.
前記内側表面層は、容器の内側（内容物を収容する側）の最表面層であり、前記外側表面層は、容器の外側（内側の反対側）の最表面層である。前記表面層は、結晶核剤を含有しない非晶状態のＰＥＴで構成される。前記表面層は、結晶核剤を含有しない非晶状態のＰＥＴのみで構成されてもよい。本容器は、前記表面層を有することにより、耐衝撃性、特に耐寒衝撃性に優れる。本書面において、「非晶状態のＰＥＴ」は、Ａ−ＰＥＴのように結晶化していない状態のＰＥＴ及びＰＥＴ−Ｇのように完全に結晶化しない状態のＰＥＴを指す。前記「非晶状態のＰＥＴ」として好ましくは、Ａ−ＰＥＴのように結晶化していない状態のＰＥＴである。 The inner surface layer is an outermost surface layer on the inner side (the side containing the contents) of the container, and the outer surface layer is an outermost surface layer on the outer side (the opposite side of the inner side) of the container. The surface layer is made of amorphous PET that does not contain a crystal nucleating agent. The surface layer may be composed of only amorphous PET containing no crystal nucleating agent. By having the surface layer, the container is excellent in impact resistance, particularly cold impact resistance. In this document, “amorphous PET” refers to PET that is not crystallized like A-PET and PET that is not completely crystallized like PET-G. The “amorphous PET” is preferably PET that is not crystallized like A-PET.
前記「非晶状態のＰＥＴ」、好ましくはＡ−ＰＥＴのＩＶ値は０．７以上、好ましくは０．７５以上である。前記ＩＶ値が上記範囲であると、優れた耐衝撃性を奏するので好ましい。 The “amorphous PET”, preferably A-PET, has an IV value of 0.7 or more, preferably 0.75 or more. It is preferable for the IV value to be in the above range since excellent impact resistance is exhibited.
前記外側表面層及び前記内側表面層の厚みの合計は、容器全体の厚みの１６％以内、好ましくは１２％以内、更に好ましくは１０％以内である。ここで、「容器全体の厚み」とは、前記外側表面層、前記内側表面層、及び前記中間層の厚みの合計を意味する。 The total thickness of the outer surface layer and the inner surface layer is within 16%, preferably within 12%, more preferably within 10% of the total thickness of the container. Here, the “total thickness of the container” means the total thickness of the outer surface layer, the inner surface layer, and the intermediate layer.
前記外側表面層及び前記内側表面層の厚みの合計が上記範囲であると、中間層のＣ−ＰＥＴによる耐熱性を確保すると共に、Ａ−ＰＥＴ等の非晶状態のＰＥＴによる光沢度及び耐衝撃性の向上を実現することができる。一般に層の厚みが薄くなると熱伝導率が良くなると考えられる。しかし、ＰＥＴは通常、結晶化速度が遅い。よって、表面層をＡ−ＰＥＴで構成した場合、表面層の厚さが薄くても、Ａ−ＰＥＴの非晶状態が維持されるため、Ａ−ＰＥＴの利点、即ち優れた光沢度及び耐衝撃性を維持できるという、当業者に全く予測し得ない意外な効果を実現することができる。本容器では、具体的には、例えば、ＪＩＳ Ｚ８７４１に準拠して６０°の角度で測定した光沢度を９８％以上とすることができる。これにより、優れた見栄えを実現することができる。 When the total thickness of the outer surface layer and the inner surface layer is within the above range, the heat resistance by C-PET of the intermediate layer is ensured, and the glossiness and impact resistance by amorphous PET such as A-PET are secured. The improvement of property can be realized. Generally, it is considered that the thermal conductivity is improved as the thickness of the layer is reduced. However, PET usually has a slow crystallization rate. Therefore, when the surface layer is composed of A-PET, even if the surface layer is thin, the amorphous state of A-PET is maintained, so the advantages of A-PET, that is, excellent glossiness and impact resistance. It is possible to realize an unexpected effect that can be maintained by a person skilled in the art, which can maintain the performance. In this container, specifically, for example, the glossiness measured at an angle of 60 ° in accordance with JIS Z8741 can be 98% or more. Thereby, the outstanding appearance can be realized.
前記外側表面層及び前記内側表面層の各厚みは同じでもよく、異なってもよい。前記外側表面層及び前記内側表面層の厚みの合計が上記範囲内である限り、前記外側表面層及び前記内側表面層の各厚みには特に限定がない。前記外側表面層及び前記内側表面層の各厚みの上限は通常８％、好ましくは６％、更に好ましくは４％である。前記外側表面層及び前記内側表面層の各厚みの下限は通常３％である。下限値が３％であると、安定して表面層厚みを持たせることができるので好ましい。 The thicknesses of the outer surface layer and the inner surface layer may be the same or different. As long as the total thickness of the outer surface layer and the inner surface layer is within the above range, each thickness of the outer surface layer and the inner surface layer is not particularly limited. The upper limit of each thickness of the outer surface layer and the inner surface layer is usually 8%, preferably 6%, and more preferably 4%. The lower limit of each thickness of the outer surface layer and the inner surface layer is usually 3%. A lower limit of 3% is preferable because the surface layer thickness can be stably provided.
前記「容器全体の厚み」については特に限定はなく、必要に応じて適宜決定することができる。前記「全体の厚み」は、例えば２０〜１０００μｍとすることができる。 The “thickness of the entire container” is not particularly limited and can be appropriately determined as necessary. The “total thickness” can be set to, for example, 20 to 1000 μm.
前記中間層及び表面層は、必要に応じて他の成分を含んでいてもよい。該他の成分として、例えば、ＰＥＴ成形容器で用いられている種々の添加剤が挙げられる。該添加剤として具体的には、例えば、着色剤、難燃剤、紫外線吸収剤、蛍光増白剤、帯電防止剤、防曇剤、滑剤、アンチブロッキング剤、耐衝撃剤、流動性改良剤、可塑剤、分散剤、及び抗菌剤が挙げられる。 The intermediate layer and the surface layer may contain other components as necessary. Examples of the other components include various additives used in PET molded containers. Specific examples of such additives include, for example, colorants, flame retardants, ultraviolet absorbers, fluorescent brighteners, antistatic agents, antifogging agents, lubricants, antiblocking agents, impact resistance agents, fluidity improvers, plasticizers. Agents, dispersants, and antibacterial agents.
本容器のＩＶ値は通常０．７以上、好ましくは０．７５以上である。シート成形により本容器を得る場合、通常、原料のＰＥＴシートのＩＶ値と本容器のＩＶ値とは同程度である。よって、原料のＰＥＴシートのＩＶ値をもって本容器のＩＶ値としてもよい。 The IV value of this container is usually 0.7 or more, preferably 0.75 or more. When this container is obtained by sheet molding, the IV value of the raw material PET sheet and the IV value of the container are generally the same. Therefore, the IV value of the raw material PET sheet may be used as the IV value of the container.
本容器の製造方法には特に限定はない。本容器は通常、本発明の製造方法により製造することができる。 There are no particular limitations on the method of manufacturing the container. This container can usually be manufactured by the manufacturing method of the present invention.
本容器の用途には特に限定はない。本容器は、例えば、飲食品包装用容器として用いることができる。上記のように、本容器は耐熱性に優れていることから、高温での使用に好適に適用できる。よって、本容器は特に、電子レンジ等による再加熱をする、半調理済みの冷凍食品用の包装用容器として好適に使用することができる。 There is no limitation in particular in the use of this container. This container can be used as a container for food and beverage packaging, for example. As described above, since this container is excellent in heat resistance, it can be suitably applied to use at high temperatures. Therefore, in particular, this container can be suitably used as a packaging container for semi-cooked frozen food that is reheated by a microwave oven or the like.
（２）ＰＥＴ成形容器の製造方法
本実施形態に係るＰＥＴ成形容器の製造方法（以下、「本方法」という。）は結晶核剤及びＩＶ＝０．７以上の非晶状態のＰＥＴを含む中間層と、結晶核剤を含有しないＩＶ＝０．７以上の非晶状態のＰＥＴで構成され、前記中間層の外側表面及び内側表面に積層された外側表面層及び内側表面層と、を有し、前記外側表面層及び内側表面層の厚みの合計が、シート全体の厚みの１６％以内である積層シートを、ＰＥＴの結晶化温度以上の温度で熱成形し、前記中間層の非晶状態のＰＥＴを結晶化する。
(2) Method for Producing PET Molded Container A method for producing a PET molded container according to this embodiment (hereinafter referred to as “the present method”) is an intermediate containing a crystal nucleating agent and an amorphous PET having an IV = 0.7 or more. A layer, and an outer surface layer and an inner surface layer that are made of PET in an amorphous state of IV = 0.7 or more that does not contain a crystal nucleating agent, and are laminated on the outer surface and the inner surface of the intermediate layer. The laminated sheet in which the total thickness of the outer surface layer and the inner surface layer is within 16% of the total thickness of the sheet is thermoformed at a temperature equal to or higher than the crystallization temperature of PET, and the intermediate layer is in an amorphous state. Crystallize the PET.
前記中間層、前記外側表面層及び前記内側表面層の内容については、本容器における説明が妥当する。本方法では、成形部材（ロール又は金型等）と接する前記表面層が結晶核剤を含有しないＡ−ＰＥＴ等の非晶状態のＰＥＴで構成されている。よって、中間層のＣ−ＰＥＴによる耐熱性を維持しつつ、結晶核剤に起因する成形部材の汚れを抑制することができ、歩留りを向上させることができる。 Regarding the contents of the intermediate layer, the outer surface layer, and the inner surface layer, the description in this container is appropriate. In this method, the surface layer in contact with the molded member (roll or mold or the like) is composed of amorphous PET such as A-PET that does not contain a crystal nucleating agent. Therefore, while maintaining the heat resistance by C-PET of the intermediate layer, it is possible to suppress the stain on the molded member due to the crystal nucleating agent, and to improve the yield.
前記積層シートを得る方法には特に限定はなく、公知のＰＥＴシートの成形方法により得ることができる。該成形方法としては、例えば、押出成形、射出成形、カレンダー成形、中空成形、真空成形、圧空成形が挙げられる。 The method for obtaining the laminated sheet is not particularly limited, and can be obtained by a known PET sheet molding method. Examples of the molding method include extrusion molding, injection molding, calendar molding, hollow molding, vacuum molding and pressure molding.
本方法により得られる容器は、上記のように、ＩＶ値が低くても優れた耐衝撃性を有する。よって、原料のＰＥＴとして、ＩＶ値が低いＰＥＴを使用することができる。また、原料のＰＥＴとして、新材ＰＥＴ（バージンＰＥＴ）若しくは再利用ＰＥＴ又はこれらの混合物を用いることができる。前記ＰＥＴとして、ＩＶ値が低いＰＥＴ又は再利用ＰＥＴを用いると、廃材量を減少させることにより環境への負荷が軽減され、また、生産コストを下げることができるので好ましい。前記再利用ポリエステル樹脂としては、例えば、工場内で発生したポリエステル樹脂の破材（例えば、容器成形時の破材）及びポリエステル樹脂含有製品から回収されたポリエステル樹脂が挙げられる。 As described above, the container obtained by this method has excellent impact resistance even if the IV value is low. Therefore, PET having a low IV value can be used as the raw material PET. Moreover, new material PET (virgin PET), reusable PET, or a mixture thereof can be used as the raw material PET. It is preferable to use PET having a low IV value or reused PET as the PET because the amount of waste material is reduced, the environmental load is reduced, and the production cost can be reduced. Examples of the recycled polyester resin include broken polyester resin material generated in a factory (for example, broken material at the time of container molding) and polyester resin recovered from a polyester resin-containing product.
本方法では、ＰＥＴの結晶化温度以上の温度で熱成形し、前記中間層の非晶状態のＰＥＴを結晶化することができる限り、容器の成形方法には特に限定はない。前記成形方法として、ポリエステル樹脂組成物について一般に採用されている公知の成形方法、具体的には、例えば、真空成形法及び圧空成形法が挙げられる。 In this method, as long as the amorphous PET in the intermediate layer can be crystallized at a temperature equal to or higher than the crystallization temperature of PET, there is no particular limitation on the method for molding the container. Examples of the molding method include known molding methods generally employed for polyester resin compositions, specifically, for example, vacuum molding and pressure molding.
前記ＰＥＴの結晶化温度以上の温度は、前記中間層の非晶状態のＰＥＴを結晶化することができる温度であれば特に限定はない。該温度は通常１５０〜２００℃である。 The temperature above the crystallization temperature of the PET is not particularly limited as long as it is a temperature at which the amorphous PET in the intermediate layer can be crystallized. The temperature is usually 150 to 200 ° C.
また、容器の成形方法において、その他の成形条件については、熱成形をすることができる限り特に限定はなく、必要に応じて適宜決定することができる。例えば、成形条件は数秒から３分程度とすることができる。本方法では、前記表面層の厚さが薄いことから、短時間の熱成形でも前記中間層の非晶状態のＰＥＴを結晶化することができ、且つ前記表面層のＡ−ＰＥＴ等の非晶状態のＰＥＴの非晶状態を維持することができる。 In the container molding method, other molding conditions are not particularly limited as long as thermoforming can be performed, and can be appropriately determined as necessary. For example, the molding conditions can be from a few seconds to about 3 minutes. In this method, since the thickness of the surface layer is thin, it is possible to crystallize the amorphous PET in the intermediate layer even by short-time thermoforming, and amorphous such as A-PET in the surface layer. The amorphous state of the PET in the state can be maintained.
以下、実施例により本発明を具体的に説明する。尚、本発明は、実施例に示す形態に限定されない。本発明の実施形態は、目的及び用途等に応じて、本発明の範囲内で種々変更することができる。 Hereinafter, the present invention will be described specifically by way of examples. In addition, this invention is not limited to the form shown in the Example. The embodiment of the present invention can be variously modified within the scope of the present invention depending on the purpose and application.
（１）ＰＥＴ成形容器の製造
原料として、以下の各成分を用いた。尚、「ＭＢ」はマスターバッチの略である。また、以下の「ＰＥＴ１」及び「ＰＥＴ２」のＩＶ値（ｄｌ／ｇ）は、ＪＩＳ Ｋ ７３６７−５に準拠して測定した。溶媒として、フェノール／１，１，２，２−テトラクロロエタン（重量比３／１）の混合溶媒を用いた。
（Ａ）ＰＥＴ１（新材）；遠東新世紀股▲分▼有限公司製「ＣＨ６１１」（ＩＶ値；１．０５ｄｌ／ｇ）
（Ｂ）ＰＥＴ２（新材）；海南逸盛石化有限公司製「ＹＳ−Ｈ０１」（ＩＶ値；０．７５ｄｌ／ｇ）
（Ｃ）結晶核剤ＭＢ；スイスＳｕｋａｎｏ社製ポリエチレン系結晶核剤「Ｓ３２０」（ポリエチレン含量；９０％）
（Ｄ）着色ＭＢ；ＰＥＴ４０％＋酸化チタン（ＴｉＯ２）６０％
(1) Production of PET molded container The following components were used as raw materials. “MB” is an abbreviation for master batch. In addition, IV values (dl / g) of the following “PET1” and “PET2” were measured in accordance with JIS K 7367-5. As a solvent, a mixed solvent of phenol / 1,1,2,2-tetrachloroethane (weight ratio 3/1) was used.
(A) PET1 (new material); “CH611” manufactured by Far East New Century Co., Ltd. (IV value; 1.05 dl / g)
(B) PET2 (new material); “YS-H01” (IV value; 0.75 dl / g) manufactured by Hainan Yusheng Petrochemical Co., Ltd.
(C) Crystal nucleating agent MB; polyethylene-based crystal nucleating agent “S320” manufactured by Sukano, Switzerland (polyethylene content: 90%)
(D) Colored MB: PET 40% + titanium oxide (TiO 2 ) 60%
表面層形成材料及び中間層形成材料中の各成分の配合割合を表１に示す。実施例１では、ＰＥＴ（新材）を表面層形成材料として使用した。比較例１及び２では、ＰＥＴ（新材）及び結晶核剤ＭＢを表１の割合で混合することにより、表面層形成材料を調製した。また、表１の割合でＰＥＴ（新材）、結晶核剤ＭＢ及び着色ＭＢを混合することにより、中間層形成用材料を調製した。 Table 1 shows the blending ratio of each component in the surface layer forming material and the intermediate layer forming material. In Example 1, PET (new material) was used as the surface layer forming material. In Comparative Examples 1 and 2, a surface layer forming material was prepared by mixing PET (new material) and crystal nucleating agent MB at the ratio shown in Table 1. Further, an intermediate layer forming material was prepared by mixing PET (new material), crystal nucleating agent MB, and colored MB in the proportions shown in Table 1.
前記中間層形成用材料及び前記表面層形成用材料を２軸押出機（株式会社プラスチック工学研究所製：型式「ＳＢＩＮ―４２―Ｓ２―３０−Ｌ」）に供給し、加工温度２８０℃で溶融混練押出しを行うことにより、ＰＥＴシートを製造した。得られたＰＥＴシートは、シート厚みが０．４０ｍｍであり、層構造が２種３層（内側表面層／中間層／外側表面層＝４／９２／４）である。 The intermediate layer forming material and the surface layer forming material are supplied to a twin-screw extruder (manufactured by Plastic Engineering Laboratory Co., Ltd. model “SBIN-42-S2-30-L”) and melted at a processing temperature of 280 ° C. A PET sheet was produced by kneading extrusion. The obtained PET sheet has a sheet thickness of 0.40 mm and a layer structure of two types and three layers (inner surface layer / intermediate layer / outer surface layer = 4/92/4).
得られたＰＥＴシートを真空成形することにより（金型温度；１６０℃、成形時間；３秒）、実施例１並びに比較例１及び２のＰＥＴ成形容器を製造した。該容器は、１２８ｍｍφ×３５ｍｍの丸型カップである。 The obtained PET sheet was vacuum molded (mold temperature: 160 ° C., molding time: 3 seconds) to produce the PET molded containers of Example 1 and Comparative Examples 1 and 2. The container is a round cup of 128 mmφ × 35 mm.
（２）性能評価
実施例１並びに比較例１及び２のＰＥＴ成形容器について、以下の方法により、耐熱性、耐寒衝撃性及び光沢度を評価した。
(2) Performance evaluation About the PET molding container of Example 1 and Comparative Examples 1 and 2, heat resistance, cold impact resistance, and glossiness were evaluated by the following methods.
（Ａ）耐熱性
ＰＥＴ成形容器に食材（グラタンソース）を入れ、２２０℃のオーブンレンジで２０分間加熱した。加熱前に、垂直に交差するように容器の直径に二方向の寸法及び容器の高さ寸法を測定し、加熱後に同じ個所の寸法を測定し、加熱前後の寸法の割合から収縮率を算出した。結果を表２に示す。表２中、「変化なし」は、収縮率が１％未満であることを意味する。
(A) Heat resistance A foodstuff (gratin sauce) was put in a PET molded container and heated in a microwave oven at 220 ° C for 20 minutes. Before heating, measure the dimensions of the container in two directions and the height of the container so that they intersect perpendicularly, measure the dimensions of the same part after heating, and calculate the shrinkage ratio from the ratio of the dimensions before and after heating . The results are shown in Table 2. In Table 2, “No change” means that the shrinkage rate is less than 1%.
表２より、実施例１のＰＥＴ成形容器では、加熱後の収縮率が１％未満であり、耐熱性に優れていることが分かる。この耐熱性試験における加熱条件（２２０℃）において、Ｃ−ＰＥＴで構成されるＰＥＴ成形容器では変形は認められないことから、実施例１のＰＥＴ成形容器は、Ｃ−ＰＥＴで構成されるＰＥＴ成形容器と同等の耐熱性を有する。 From Table 2, it can be seen that in the PET molded container of Example 1, the shrinkage after heating is less than 1%, and the heat resistance is excellent. Under the heating conditions (220 ° C.) in this heat resistance test, no deformation is observed in the PET molded container composed of C-PET, so the PET molded container of Example 1 is PET molded composed of C-PET. It has the same heat resistance as the container.
（Ｂ）耐寒衝撃性
ＰＥＴ成形容器に水を入れて、−３０℃雰囲気下で２日間保管することにより凍らせた。その後、ＰＥＴ成形容器を段ボール箱に入れて（梱包数；容器６個×２段積み＝１２個）、箱ごと水平に落下させ（落下高さ；１．５ｍ及び２ｍ）、落下後に箱の中にある容器の割れ個数を確認した。各条件について２回ずつ試験を行った。結果を表３に示す。
(B) Cold impact resistance Water was put into a PET molded container and frozen by storing in a −30 ° C. atmosphere for 2 days. After that, put the PET molded container in a cardboard box (packing number; 6 containers x 2 stacks = 12) and drop the whole box horizontally (fall height: 1.5m and 2m) The number of cracks in the container was confirmed. The test was performed twice for each condition. The results are shown in Table 3.
表３より、実施例１は、ＩＶ値が同程度の比較例２と比べて容器の割れ個数が少なく、実施例１よりもＩＶ値が大きい比較例１と同程度の結果であった。よって、実施例１は、ＩＶ値が低くても優れた耐衝撃性を有する。 From Table 3, Example 1 had the same number of cracks in the container as Comparative Example 2 having the same IV value, and the same result as Comparative Example 1 having a larger IV value than Example 1. Therefore, Example 1 has excellent impact resistance even when the IV value is low.
（Ｃ）光沢度
測定機（日本電色工業製「ＶＧ７０００」）を用いて、ＰＥＴ成形容器の内面の光沢度を測定した。測定方法は、ＪＩＳ Ｚ ８７４１に準拠して、入射・受光角度を６０°として測定を行った。また、参考として、Ａ−ＰＥＴ成形容器の内面の光沢度も測定した。これらの結果を表４に示す。
(C) Glossiness The glossiness of the inner surface of the PET molded container was measured using a measuring instrument (“VG7000” manufactured by Nippon Denshoku Industries Co., Ltd.). The measurement was performed according to JIS Z 8741 with the incident / light receiving angle set to 60 °. For reference, the glossiness of the inner surface of the A-PET molded container was also measured. These results are shown in Table 4.
表４より、実施例１の光沢度は、比較例１及び２の光沢度よりも優れ、Ａ−ＰＥＴ成形容器と同等の光沢度であることが分かる。実施例及び比較例の結果の差異は、表面の平滑性によるもの（前者は後者よりも平滑性に優れる。）と考えられる（これは発明者個人の見解の表明であり、発明を限定する趣旨の記載ではない。）。 From Table 4, it can be seen that the glossiness of Example 1 is superior to that of Comparative Examples 1 and 2 and is equivalent to that of the A-PET molded container. The difference between the results of the examples and the comparative examples is considered to be due to the smoothness of the surface (the former is superior to the latter in terms of smoothness) (this is an expression of the inventor's personal opinion, and is intended to limit the invention) Is not described.)
Claims (3)
前記外側表面層及び内側表面層の厚みの合計が、容器全体の厚みの１６％以内であることを特徴とする、ＰＥＴ成形容器。 An intermediate layer containing crystalline PET, and an outer surface layer and an inner surface layer made of amorphous PET not containing a crystal nucleating agent and laminated on the outer surface and the inner surface of the intermediate layer,
The PET molded container, wherein the total thickness of the outer surface layer and the inner surface layer is within 16% of the total thickness of the container.
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Citations (5)
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|---|---|---|---|---|
| JPH05212840A (en) * | 1992-02-04 | 1993-08-24 | Ajinomoto Co Inc | Heat-sealable polyester sheet |
| JP2907685B2 (en) * | 1993-06-28 | 1999-06-21 | 積水化成品工業株式会社 | Polyethylene terephthalate sheet molded heat-resistant container and method for producing the same |
| JP2005289472A (en) * | 2004-04-01 | 2005-10-20 | Lining Container Kk | Thermoformed multi-layer container and manufacturing method thereof |
| JP2006312485A (en) * | 2005-05-09 | 2006-11-16 | Ryoji Odate | Multilayered structure resin container |
| JP4223700B2 (en) * | 2001-06-29 | 2009-02-12 | 株式会社吉野工業所 | Manufacturing method of heat-resistant PET container |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05212840A (en) * | 1992-02-04 | 1993-08-24 | Ajinomoto Co Inc | Heat-sealable polyester sheet |
| JP2907685B2 (en) * | 1993-06-28 | 1999-06-21 | 積水化成品工業株式会社 | Polyethylene terephthalate sheet molded heat-resistant container and method for producing the same |
| JP4223700B2 (en) * | 2001-06-29 | 2009-02-12 | 株式会社吉野工業所 | Manufacturing method of heat-resistant PET container |
| JP2005289472A (en) * | 2004-04-01 | 2005-10-20 | Lining Container Kk | Thermoformed multi-layer container and manufacturing method thereof |
| JP2006312485A (en) * | 2005-05-09 | 2006-11-16 | Ryoji Odate | Multilayered structure resin container |
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