JP2022009813A - Laminate provided with resin layer derived from biomass and adiabatic container - Google Patents

Laminate provided with resin layer derived from biomass and adiabatic container Download PDF

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JP2022009813A
JP2022009813A JP2021178655A JP2021178655A JP2022009813A JP 2022009813 A JP2022009813 A JP 2022009813A JP 2021178655 A JP2021178655 A JP 2021178655A JP 2021178655 A JP2021178655 A JP 2021178655A JP 2022009813 A JP2022009813 A JP 2022009813A
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density
layer
biomass
polyolefin resin
polyethylene resin
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友央 上野
Tomohiro Ueno
嘉貢 西野
Yoshitsugu NISHINO
宏行 高野
Hiroyuki Takano
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Nissin Foods Holdings Co Ltd
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Nissin Foods Holdings Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/46—Applications of disintegrable, dissolvable or edible materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
    • B65D81/38—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents with thermal insulation

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Wrappers (AREA)
  • Laminated Bodies (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing a laminate and a foam laminate small in environmental load and excellent in the adiabatic property.
SOLUTION: The present invention relates to a foam laminate provided with, at least, a foam layer made of a low density polyolefin resin having the density of 0.91 g/cm3 or larger and smaller than 0.93 g/cm3, a paper substrate layer, and a non-foam layer made of a medium to high density polyolefin resin having the density of 0.93 g/cm3 or larger and 0.97 g/cm3 or smaller in this order, the low density polyolefin resin and/or the medium to high density polyolefin resin containing a biomass polyethylene resin, and the degree of biomass being 5% or larger.
SELECTED DRAWING: Figure 1
COPYRIGHT: (C)2022,JPO&INPIT

Description

本発明は、バイオマス由来の樹脂層を備えた積層体、発泡積層体及び発泡断熱容器に関するものである。 The present invention relates to a laminate having a resin layer derived from biomass, an effervescent laminate, and an effervescent heat insulating container.

カップ麺用の容器、コーヒーカップ等の飲食用容器では、一般的に断熱容器が使用されている。従来、この用途に使用される断熱容器としては、発泡ポリスチレン製の容器が知られていたが、容器全体を発泡させているため嵩が大きく、ゴミが増加するという問題があった。また、紙製の容器比べると強度が低く、硬い内容物（麺塊等）を入れたまま輸送すると破損しやすいという課題があった。 Insulation containers are generally used in containers for cup noodles and food and drink containers such as coffee cups. Conventionally, as a heat insulating container used for this purpose, a container made of expanded polystyrene has been known, but there is a problem that the container is bulky and dust increases because the entire container is foamed. In addition, the strength is lower than that of a paper container, and there is a problem that it is easily damaged when transported with hard contents (noodle lumps, etc.) in it.

この課題を解決するため、紙容器の外壁面に低融点のポリエチレン樹脂をラミネートして、加熱することにより、基材である紙に含まれている水分の蒸気圧を利用してポリエチレン樹脂を発泡させて発泡断熱シートを製造する技術が開示されている（特許文献１～３）。 In order to solve this problem, a polyethylene resin with a low melting point is laminated on the outer wall surface of the paper container and heated to foam the polyethylene resin using the vapor pressure of the water contained in the paper as the base material. Disclosed is a technique for producing a foamed heat insulating sheet (Patent Documents 1 to 3).

一方、持続可能な開発目標（ＳＤＧｓ）を達成すべく、化石燃料からの脱却が望まれており、その一つの手段としてバイオマス素材の活用が提案されている。例えば、ポリ乳酸（ＰＬＡ）について商業化が進んでいる。 しかしながら、プラスチックとしての特性がポリエチレンやＰＥＴのような汎用プラスチックと大きく異なるため、ＰＬＡが用いられる用途は一部に限られていた。 On the other hand, in order to achieve the Sustainable Development Goals (SDGs), it is desired to break away from fossil fuels, and the use of biomass materials has been proposed as one of the means. For example, polylactic acid (PLA) is being commercialized. However, since the properties as a plastic are significantly different from those of general-purpose plastics such as polyethylene and PET, the use of PLA has been limited to some.

そこで、穀物からバイオエタノールを製造し、これをエチレンガスに変えて、様々なプラスチック（ポリエチレン、ＰＥＴの原料であるエチレングリコール）の原料として用いる方法が提案されている。ところが、このようなプラスチックについて、現行製品からの代替が可能なのかどうかについては十分に検討がなされてこなかった。 Therefore, a method has been proposed in which bioethanol is produced from grains, converted into ethylene gas, and used as a raw material for various plastics (polyethylene, ethylene glycol which is a raw material for PET). However, it has not been fully examined whether such plastics can be replaced with the current products.

特開２００６－２８２２５７公報Japanese Unexamined Patent Publication No. 2006-282257 特開２０１４－１３３３３７公報Japanese Unexamined Patent Publication No. 2014-133337 特開２０１５－２１４３６５号公報Japanese Unexamined Patent Publication No. 2015-214365

本発明は、上記のような事情に鑑みてなされたものであり、環境負荷が小さく、断熱性が良好な積層体および発泡積層体を製造することにある。 The present invention has been made in view of the above circumstances, and an object of the present invention is to produce a laminated body and a foamed laminated body having a small environmental load and good heat insulating properties.

本発明者らは、少なくとも、密度0.91g/cm3以上、0.93g/cm3未満の低密度ポリオレフィン樹脂からなる発泡層と、紙基材層と、密度0.93g/cm3以上、0.97g/cm3以下の中高密度ポリオレフィン樹脂からなる非発泡層とを順に備える発泡積層体であって、低密度ポリオレフィン樹脂および／または中高密度ポリオレフィン樹脂がバイオマスポリエチレン樹脂を含み、且つバイオマス度が５％以上であることを特徴とする積層体により上記課題を解決し得ることを見出した。 The present inventors have at least a foam layer made of a low-density polyolefin resin having a density of 0.91 g / cm 3 or more and less than 0.93 g / cm 3 , a paper substrate layer, and a density of 0.93 g / cm 3 or more and 0.97 g /. A foamed laminate comprising a non-foamed layer made of a medium-density polyolefin resin of cm 3 or less in order, wherein the low-density polyolefin resin and / or the medium-high-density polyolefin resin contains a biomass polyethylene resin and has a biomass degree of 5% or more. It has been found that the above-mentioned problems can be solved by a laminated body characterized by being present.

本発明の完成により、環境負荷が小さく、断熱性が良好な積層体、発泡積層体及び発泡断熱容器を製造することが可能となった。 With the completion of the present invention, it has become possible to manufacture a laminate, an effervescent laminate, and an effervescent heat insulating container having a small environmental load and good heat insulating properties.

実施例１の構成（発泡前）を断面図で説明したものである。The configuration (before foaming) of Example 1 is described in a cross-sectional view. 実施例６の構成（発泡前）を断面図で説明したものである。The configuration (before foaming) of Example 6 is described in a cross-sectional view.

本発明は、少なくとも、密度0.91g/cm3以上、0.93g/cm3未満の低密度ポリオレフィン樹脂からなる発泡層と、紙基材層と、密度0.93g/cm3以上、0.97g/cm3以下の中高密度ポリオレフィン樹脂からなる非発泡層とを順に備える発泡積層体であって、低密度ポリオレフィン樹脂および／または中高密度ポリオレフィン樹脂がバイオマスポリエチレン樹脂を含み、且つバイオマス度が５％以上であることを特徴とする積層体に関するものである。以下、詳細について説明を行う。 The present invention comprises a foam layer made of a low density polyolefin resin having a density of 0.91 g / cm 3 or more and a density of less than 0.93 g / cm 3 , a paper substrate layer, and a density of 0.93 g / cm 3 or more and 0.97 g / cm 3 . A foamed laminate comprising the following non-foamed layers made of medium-density polyolefin resin in order, wherein the low-density polyolefin resin and / or the medium-high density polyolefin resin contains a biomass polyethylene resin and has a biomass degree of 5% or more. It relates to a laminated body characterized by. The details will be described below.

紙基材
本発明の積層体を構成する紙基材には特に限定はないが、非塗工紙、塗工紙などを使用することができる。また、容器としての強靭さを実現する観点から紙基材の坪量は150～400g/m２好ましく、更に好ましくは、250～350g/m２である。さらに、ポリエチレンを好適に発泡させる観点から紙基材に含まれる水分は5～10重量％が好ましく、6～8重量％がより好ましい。 Paper base material The paper base material constituting the laminate of the present invention is not particularly limited, but uncoated paper, coated paper, or the like can be used. Further, from the viewpoint of realizing toughness as a container, the basis weight of the paper base material is preferably 150 to 400 g / m 2 , and more preferably 250 to 350 g / m 2 . Further, from the viewpoint of preferably foaming polyethylene, the water content in the paper substrate is preferably 5 to 10% by weight, more preferably 6 to 8% by weight.

非塗工紙は、原料パルプにクレー、タルク、二酸化チタン、炭酸カルシウム、水酸化アルミニウム粉末等の填料を加え、必要に応じてサイズ剤、紙力増強剤、定着剤等を添加して製造することができる。また、紙面強度を向上させるため、スチレン系樹脂、スチレン・マレイン酸樹脂、澱粉、カルボキシメチル化セルロース、ポリビニルアルコール、ポリアクリルアミド等の薬品を表面に塗工してもよい。 Uncoated paper is manufactured by adding fillers such as clay, talc, titanium dioxide, calcium carbonate, aluminum hydroxide powder, etc. to the raw material pulp, and adding sizing agents, paper strength enhancers, fixing agents, etc. as necessary. be able to. Further, in order to improve the paper surface strength, a chemical such as a styrene resin, a styrene / maleic acid resin, starch, carboxymethylated cellulose, polyvinyl alcohol, or polyacrylamide may be applied to the surface.

塗工紙としては、炭酸カルシウム、二酸化チタン、水酸化アルミニウム等の顔料と、ポリビニルアルコール、スチレン・ブタジエンラテックス、メチルメタクリレート・ブタジエンラテックス等の接着剤とを含む塗工液を調整し、表面に塗工することで得ることができる。 As the coated paper, a coating liquid containing a pigment such as calcium carbonate, titanium dioxide, aluminum hydroxide and an adhesive such as polyvinyl alcohol, styrene / butadiene latex, and methylmethacrylate / butadiene latex is prepared and applied to the surface. It can be obtained by working.

発泡層
本発明において発泡層は、密度0.91g/cm3以上、0.93g/cm3未満の低密度ポリオレフィン樹脂からなる。発泡層に融点の低い低密度ポリオレフィン樹脂を用いることで、発泡加工の際に、非発泡層を発泡させることなく、発泡層のみを発泡させることができる。 Foamed layer In the present invention, the foamed layer is made of a low-density polyolefin resin having a density of 0.91 g / cm 3 or more and less than 0.93 g / cm 3 . By using a low-density polyolefin resin having a low melting point for the foamed layer, it is possible to foam only the foamed layer without foaming the non-foamed layer during the foaming process.

さらに、本発明においては、前記低密度ポリオレフィン樹脂および／または中高密度ポリオレフィン樹脂がバイオマスポリエチレン樹脂を含み、且つバイオマス度が５％以上であることが必要である。 Further, in the present invention, it is necessary that the low-density polyolefin resin and / or the medium-high-density polyolefin resin contains a biomass polyethylene resin and has a biomass degree of 5% or more.

ここで、バイオマスポリエチレン樹脂とは、植物由来のエチレンから合成されたポリエチレン樹脂を指す。なお、植物由来のエチレンは、植物（トウモロコシ、サトウキビ、タピオカ等）を発酵させて得られたエタノール等を原料として、周知の方法により製造することができる。 Here, the biomass polyethylene resin refers to a polyethylene resin synthesized from plant-derived ethylene. The plant-derived ethylene can be produced by a well-known method using ethanol or the like obtained by fermenting a plant (corn, sugar cane, tapioca, etc.) as a raw material.

また、「バイオマス度」（ポリオレフィン樹脂中のバイオマス由来の炭素濃度）とは、放射性炭素（Ｃ１４）測定によりバイオマス由来の炭素の含有量を測定した値である。大気中の二酸化炭素にはＣ１４が一定量含まれており、大気中の二酸化炭素を取り入れて成長する植物のＣ１４の含有量も同程度である。一方、化石燃料にはＣ１４が殆ど含まれていない。したがって、ポリオレフィン樹脂に含まれるＣ１４の割合を測定することにより、ポリオレフィン樹脂中のバイオマス由来の炭素濃度「バイオマス度」を算出することができる。 The "biomass degree" (carbon concentration derived from biomass in the polyolefin resin) is a value obtained by measuring the carbon content derived from biomass by measuring radioactive carbon (C14). Carbon dioxide in the atmosphere contains a certain amount of C14, and the content of C14 in plants that grow by taking in carbon dioxide in the atmosphere is about the same. On the other hand, fossil fuel contains almost no C14. Therefore, by measuring the ratio of C14 contained in the polyolefin resin, the carbon concentration "biomass degree" derived from biomass in the polyolefin resin can be calculated.

具体的には、ポリエチレン樹脂を、バイオマス由来のエチレンのみで製造すれば、バイオマス度は１００％となり、化石燃料由来の原料のみで製造すればバイオマス度は０％となる。 Specifically, if the polyethylene resin is produced only from ethylene derived from biomass, the biomass degree is 100%, and if it is produced only from the raw material derived from fossil fuel, the biomass degree is 0%.

低密度ポリエチレン樹脂のメルトフローレート（以下、「ＭＦＲ」という場合がある）は、8～28g/10分が好ましく、10～20g/10分がより好ましい。この範囲であれば、ポリエチレン樹脂の発泡が安定するため、断熱性や発泡後の外観が良好である。 The melt flow rate of the low-density polyethylene resin (hereinafter, may be referred to as “MFR”) is preferably 8 to 28 g / 10 minutes, more preferably 10 to 20 g / 10 minutes. Within this range, the foaming of the polyethylene resin is stable, so that the heat insulating property and the appearance after foaming are good.

非発泡層
本発明において非発泡層は、密度0.93g/cm3以上、0.97g/cm3以下の中高密度ポリオレフィン樹脂からなる。非発泡層に融点の高い中高密度ポリオレフィン樹脂を用いることで、発泡加工の際に、非発泡層を発泡させることなく、発泡層のみを発泡させることができる。 Non-foaming layer In the present invention, the non-foaming layer is made of a medium-high density polyolefin resin having a density of 0.93 g / cm 3 or more and 0.97 g / cm 3 or less. By using a medium-high-density polyolefin resin having a high melting point for the non-foaming layer, it is possible to foam only the foamed layer without foaming the non-foaming layer during the foaming process.

さらに、本発明においては、前記低密度ポリオレフィン樹脂および／または中高密度ポリオレフィン樹脂がバイオマスポリエチレン樹脂を含み、且つバイオマス度が５％以上であることが必要である。 Further, in the present invention, it is necessary that the low-density polyolefin resin and / or the medium-high-density polyolefin resin contains a biomass polyethylene resin and has a biomass degree of 5% or more.

さらに、紙基材層と、非発泡層の間に、中間層を設けることもできる。中間層としては、ポリ乳酸フィルム、PETフィルム、CPPフィルム、OPPフィルムおよびナイロンフィルム等、並びにこれらのフィルムに酸化アルミニウム等を蒸着したバリアフィルムなどを適宜選択して用いることができる。なお、これらのフィルムには、化石燃料由来の原料であるか、植物由来の原料であるかを問わず、いずれも好適に用いることができる。 Further, an intermediate layer may be provided between the paper base material layer and the non-foaming layer. As the intermediate layer, a polylactic acid film, a PET film, a CPP film, an OPP film, a nylon film or the like, and a barrier film obtained by depositing aluminum oxide or the like on these films can be appropriately selected and used. It should be noted that any of these films can be suitably used regardless of whether the film is a fossil fuel-derived raw material or a plant-derived raw material.

押出ラミネート条件
押出ラミネートの方法としては、シングルラミネート法、タンデムラミネート法、サンドウィッチラミネート法、共押出ラミネート法などを適宜選択することができる。 Extrusion Laminating Conditions As the extrusion laminating method, a single laminating method, a tandem laminating method, a sandwich laminating method, a coextruding laminating method, or the like can be appropriately selected.

ラミネート時のポリエチレン樹脂の（Tダイ直下）温度としては、260～350℃が好ましく、280～330℃がより好ましい。この範囲であれば、ポリエチレン樹脂層と紙基材間のラミネート強度や、発泡後の外観を好適なものとすることができる。また、冷却ロールの表面温度は10～50℃の範囲で制御することが好ましい。 The temperature of the polyethylene resin (immediately below the T die) at the time of laminating is preferably 260 to 350 ° C, more preferably 280 to 330 ° C. Within this range, the lamination strength between the polyethylene resin layer and the paper substrate and the appearance after foaming can be made suitable. Further, it is preferable to control the surface temperature of the cooling roll in the range of 10 to 50 ° C.

ラミネート後（発泡前）のポリエチレン樹脂層の厚みには特に限定はないが、30～150μmが好ましく、40～100μmがより好ましい。この範囲であれば、発泡後のポリエチレン樹脂層に充分な厚みを持たせることができるため、断熱性が良好である。 The thickness of the polyethylene resin layer after laminating (before foaming) is not particularly limited, but is preferably 30 to 150 μm, more preferably 40 to 100 μm. Within this range, the polyethylene resin layer after foaming can have a sufficient thickness, so that the heat insulating property is good.

また、引取速度が遅すぎると、生産性が悪いため、引取速度は40m/分以上が好ましく、60m/分がより好ましい。
一方、引取速度が速すぎると、ポリエチレン樹脂がネックインしやすく生産性が低下しやすい。したがって、引張速度は130m／分以下が好ましく、110m/分以下がより好ましい。 Further, if the pick-up speed is too slow, the productivity is poor, so the pick-up speed is preferably 40 m / min or more, more preferably 60 m / min.
On the other hand, if the take-up speed is too fast, the polyethylene resin tends to be necked in and the productivity tends to decrease. Therefore, the tensile speed is preferably 130 m / min or less, more preferably 110 m / min or less.

次に、エアギャップについて説明する。ここで、エアギャップとはTダイの押出口からニップロールまでの距離を指す。 Next, the air gap will be described. Here, the air gap refers to the distance from the T-die extrusion port to the nip roll.

ラミネート加工時のエアギャップを広げすぎるとポリエチレン樹脂がネックインして生産性が低下すため、エアギャップは250mm以下が好ましく、200mm以下がより好ましい。 If the air gap during laminating is widened too much, the polyethylene resin will neck in and productivity will decrease. Therefore, the air gap is preferably 250 mm or less, more preferably 200 mm or less.

本発明では、ポリエチレン樹脂がエアギャップを通過している間に、オゾンガス及び／又は酸素ガスで表面処理することが好ましい。オゾンガス及び／又は酸素ガスで表面処理することにより、酸化被膜の形成を促進し、基材層との接着力を向上させることができる。オゾンガス及び／又は酸素ガスの処理量には特に限定はないが、ポリエチレン樹脂の酸化を促進する観点で0.5mg/m2以上が好ましい。 In the present invention, it is preferable to surface-treat the polyethylene resin with ozone gas and / or oxygen gas while passing through the air gap. By surface-treating with ozone gas and / or oxygen gas, the formation of an oxide film can be promoted and the adhesive force with the substrate layer can be improved. The amount of ozone gas and / or oxygen gas to be treated is not particularly limited, but 0.5 mg / m 2 or more is preferable from the viewpoint of promoting the oxidation of the polyethylene resin.

ポリエチレン樹脂
低密度ポリエチレン樹脂および高密度ポリエチレン樹脂として、ブラスケム社製のバイオマスポリエチレンを用いて、バイオマス由来のポリエチレン樹脂（B-LDPE、B-HDPE1～3）を調整した。ポリエチレン樹脂の密度（g/cm3）は表１の通りである。 Polyethylene resin As the low-density polyethylene resin and the high-density polyethylene resin, biomass polyethylene manufactured by Brasschem Co., Ltd. was used to prepare polyethylene-derived polyethylene resins (B-LDPE, B-HDPE1 to 3). The density of polyethylene resin (g / cm 3 ) is as shown in Table 1.

Figure 2022009813000002
Figure 2022009813000002

実施例１
（工程１）紙基材の片面に、B-HDPE1を押出ラミネートによって積層し、厚さ40μｍの非発泡層を設けた。（工程２）紙基材の非発泡層とは逆の面に、B-LDPEを押出ラミネートによって積層し、厚さ70μｍの発泡層（発泡加工前）を設けて、積層体（実施例１）を製造した。加工条件の詳細は以下の通りである。 Example 1
(Step 1) B-HDPE1 was laminated by extrusion laminating on one side of a paper substrate to provide a non-foamed layer having a thickness of 40 μm. (Step 2) B-LDPE is laminated by extrusion laminating on the surface opposite to the non-foaming layer of the paper substrate, and a foaming layer (before foaming) having a thickness of 70 μm is provided to provide a laminated body (Example 1). Manufactured. The details of the processing conditions are as follows.

（工程１）
紙基材：水分量23g/m2、坪量320g/m2
押出温度（Tダイ出口温度）：320℃
引取速度（ラミネート速度）：60m/分
エアギャップ：80mm (Step 1)
Paper substrate: Moisture content 23 g / m 2 , Basis weight 320 g / m 2
Extrusion temperature (T die outlet temperature): 320 ° C
Pick-up speed (lamination speed): 60m / min Air gap: 80mm

（工程２）
押出温度（Tダイ出口温度）：310℃
引取速度（ラミネート速度）：60m/分
エアギャップ：80mm (Step 2)
Extrusion temperature (T die outlet temperature): 310 ° C
Pick-up speed (lamination speed): 60m / min Air gap: 80mm

実施例２～５
発泡層及び非発泡層に用いる素材を表２の通り変更して実施例２～５を製造した。なお、素材以外の条件（押出温度、引取速度等）は実施例１と同様である。 Examples 2-5
Examples 2 to 5 were manufactured by changing the materials used for the foamed layer and the non-foamed layer as shown in Table 2. The conditions other than the material (extrusion temperature, take-up speed, etc.) are the same as in Example 1.

比較例１
実施例１におけるB-HDPE1をペトロセンLW04-1に、B-LDPEをペトロセン07C03Cに変更して比較例１を製造した。なお、素材以外の条件（押出温度、引取速度等）は実施例１と同様である。 Comparative Example 1
Comparative Example 1 was manufactured by changing B-HDPE1 in Example 1 to Petrosen LW04-1 and B-LDPE to Petrosen 07C03C. The conditions other than the material (extrusion temperature, take-up speed, etc.) are the same as in Example 1.

ペトロセンLW04-1およびペトロセン07C03Cの詳細は以下の通りである。
ペトロセンLW04-1：東ソー社製、化石燃料由来の中密度ポリエチレン樹脂、ＭＦＲ4.3g/10分、密度940kg/m3
ペトロセン07C03C：東ソー社製、化石燃料由来の低密度ポリエチレン樹脂、ＭＦＲ 14g/10分、密度918kg/m3 Details of Petrosen LW04-1 and Petrosen 07C03C are as follows.
Petrosen LW04-1: Tosoh, medium density polyethylene resin derived from fossil fuel, MFR 4.3g / 10 minutes, density 940kg / m 3
Petrosen 07C03C: Tosoh, low density polyethylene resin derived from fossil fuel, MFR 14g / 10 minutes, density 918kg / m 3

Figure 2022009813000003
Figure 2022009813000003

発泡工程
積層体（実施例１～５及び比較例１）を１２０℃で6分間加熱して、発泡層を形成した。 Foaming Step The laminate (Examples 1 to 5 and Comparative Example 1) was heated at 120 ° C. for 6 minutes to form a foamed layer.

実施例１～５のラミネート後（発泡工程前）の外観、及び発泡工程後の外観は、いずれも比較例１と同様に良好であり、バイオマス原料を用いることによる差はなかった。 The appearance of Examples 1 to 5 after laminating (before the foaming step) and after the foaming step were both as good as in Comparative Example 1, and there was no difference due to the use of the biomass raw material.

実施例１～５の発泡層と非発泡層について、比較例１を基準に、以下の通り外観を評価した。
発泡層（ラミネート後、発泡工程前）：比較例１と比較して、ポリエチレン樹脂層の厚みに斑がないかどうかを確認し、比較例１と同等以上の場合には“良好”とした。
発泡層（発泡工程後）：比較例１と比較して、発泡層が均一に発泡しているかどうか、凹凸が目立つかどうかを確認し、比較例１と同等以上の場合には“良好”とした。
非発泡層：比較例１と比較して、ポリエチレン樹脂層の厚みに斑がないかどうかを確認し、比較例１と同等以上の場合には“良好”とした。 The appearance of the foamed layer and the non-foamed layer of Examples 1 to 5 was evaluated as follows based on Comparative Example 1.
Foamed layer (after laminating, before foaming step): Compared with Comparative Example 1, it was confirmed whether the thickness of the polyethylene resin layer was uneven, and when it was equal to or higher than that of Comparative Example 1, it was evaluated as “good”.
Foamed layer (after foaming step): Compared with Comparative Example 1, it was confirmed whether the foamed layer was uniformly foamed and whether the unevenness was conspicuous, and when it was equal to or higher than that of Comparative Example 1, it was "good". did.
Non-foamed layer: Compared with Comparative Example 1, it was confirmed whether the thickness of the polyethylene resin layer was uneven, and when it was equal to or higher than that of Comparative Example 1, it was regarded as “good”.

実施例６
（工程１－１）紙基材及び貼り合わせ面にアンカーコート剤を塗布したPETフィルム（東洋紡社製、E5100、12μｍ）を、ペトロセンLW14A（15μm）を押出ラミネートして貼り合わせた。（工程１－２）PETフィルム側の非積層面にアンカーコート剤を塗布した後に、ペトロセンLW14A（20μｍ、PETフィルム側）及びB-HDPE3（20μm）を共押出ラミネートによって積層し、非発泡層を設けた。（工程２）紙基材の非発泡層とは逆の面に、B-LDPEを押出ラミネートによって積層し、厚さ70μｍの発泡層（発泡加工前）を設けて、積層体（実施例６）を製造した。 Example 6
(Step 1-1) A PET film (manufactured by Toyobo Co., Ltd., E5100, 12 μm) coated with an anchor coating agent on a paper substrate and a bonded surface was extruded and laminated with Petrosen LW14A (15 μm) and bonded. (Step 1-2) After applying the anchor coating agent to the non-laminated surface on the PET film side, petrosene LW14A (20 μm, PET film side) and B-HDPE3 (20 μm) are laminated by coextrusion laminating to form a non-foamed layer. Provided. (Step 2) B-LDPE is laminated by extrusion laminating on the surface opposite to the non-foaming layer of the paper substrate, and a foaming layer (before foaming) having a thickness of 70 μm is provided to provide a laminated body (Example 6). Manufactured.

E5100及びペトロセンLW14Aの詳細は以下の通りである。
E5100：東洋紡社製、化石燃料由来のポリエチレンテレフタレート樹脂、厚さ12μｍ
ペトロセンLW14A：東ソー社製、化石燃料由来の中密度ポリエチレン樹脂、ＭＦＲ10g/10分、密度933kg/m3 Details of the E5100 and Petrosen LW14A are as follows.
E5100: Polyethylene terephthalate resin derived from fossil fuel manufactured by Toyobo Co., Ltd., thickness 12 μm
Petrosen LW14A: Tosoh, medium density polyethylene resin derived from fossil fuel, MFR 10g / 10 minutes, density 933kg / m 3

（工程１－１）
紙基材：水分量23g/m2、坪量320g/m2
押出温度（Tダイ出口温度）：320℃
引取速度（ラミネート速度）：80m/分
エアギャップ：130mm (Step 1-1)
Paper substrate: Moisture content 23 g / m 2 , Basis weight 320 g / m 2
Extrusion temperature (T die outlet temperature): 320 ° C
Pick-up speed (lamination speed): 80m / min Air gap: 130mm

（工程１－２）
アンカーコート剤：東洋モートン社製、EL-540/CAT-RT32
押出温度（Tダイ出口温度）：320℃
引取速度（ラミネート速度）：80m/分
エアギャップ：130mm (Step 1-2)
Anchor coating agent: manufactured by Toyo Morton, EL-540 / CAT-RT32
Extrusion temperature (T die outlet temperature): 320 ° C
Pick-up speed (lamination speed): 80m / min Air gap: 130mm

（工程２）
押出温度（Tダイ出口温度）：310℃
引取速度（ラミネート速度）：60m/分
エアギャップ：80mm
発泡層（発泡加工前）の厚さ：70μm (Step 2)
Extrusion temperature (T die outlet temperature): 310 ° C
Pick-up speed (lamination speed): 60m / min Air gap: 80mm
Thickness of foam layer (before foaming): 70 μm

実施例７
実施例６におけるB-HDPE3をペトロセンLW04-1に変更して、実施例７を製造した。 Example 7
B-HDPE3 in Example 6 was changed to Petrosen LW04-1 to produce Example 7.

比較例２
実施例６におけるB-HDPE3をペトロセンLW04-1に、B-LDPEをペトロセン07C03Cにそれぞれ変更して比較例２を製造した。 Comparative Example 2
Comparative Example 2 was manufactured by changing B-HDPE3 in Example 6 to Petrosen LW04-1 and B-LDPE to Petrosen 07C03C.

発泡工程
積層体（実施例６、実施例７及び比較例２）を１２０℃で6分間加熱して、発泡層を形成した。 Foaming Step The laminate (Example 6, Example 7 and Comparative Example 2) was heated at 120 ° C. for 6 minutes to form a foamed layer.

発泡のタイミングや速度に多少の差はあるものの、発泡工程後の実施例６及び実施例７の外観は、比較例２と同様に良好であり、バイオマス原料を用いることによる差はなかった。 Although there were some differences in the timing and speed of foaming, the appearances of Examples 6 and 7 after the foaming step were as good as in Comparative Example 2, and there was no difference due to the use of the biomass raw material.

実施例６，７の発泡層と非発泡層について、比較例２を基準に、以下の通り外観を評価した。
発泡層（ラミネート後、発泡工程前）：比較例２と比較して、ポリエチレン樹脂層の厚みに斑がないかどうかを確認し、比較例２と同等以上の場合には“良好”とした。
発泡層（発泡工程後）：比較例２と比較して、発泡層が均一に発泡しているかどうか、凹凸が目立つかどうかを確認し、比較例２と同等以上の場合には“良好”とした。
非発泡層：比較例２と比較して、ポリエチレン樹脂層の厚みに斑がないかどうかを確認し、比較例１と同等以上の場合には“良好”とした。 The appearance of the foamed layer and the non-foamed layer of Examples 6 and 7 was evaluated as follows based on Comparative Example 2.
Foamed layer (after laminating, before foaming step): Compared with Comparative Example 2, it was confirmed whether the thickness of the polyethylene resin layer was uneven, and when it was equal to or higher than that of Comparative Example 2, it was evaluated as “good”.
Foamed layer (after foaming step): Compared with Comparative Example 2, it was confirmed whether the foamed layer was uniformly foamed and whether the unevenness was conspicuous, and when it was equal to or higher than that of Comparative Example 2, it was "good". did.
Non-foamed layer: Compared with Comparative Example 2, it was confirmed whether the thickness of the polyethylene resin layer was uneven, and when it was equal to or higher than that of Comparative Example 1, it was regarded as “good”.

その他の実施例
バイオマス由来のポリエチレン樹脂を、バイオマス由来のポリエチレン樹脂及び化石燃料由来のポリエチレン樹脂を併用したポリエチレン樹脂に置き換えて前記同様の実験を行った。詳細は以下の通りである。 Other Examples The same experiment as described above was carried out by replacing the polyethylene resin derived from biomass with a polyethylene resin using a polyethylene resin derived from biomass and a polyethylene resin derived from fossil fuel in combination. The details are as follows.

まず、実施例３におけるB-LDPEを、B-LDPEとペトロセン07C03Cとの混合物に変更して、実施例８～１８を製造した。混合物の配合比及び評価結果は表３の通りである。 First, B-LDPE in Example 3 was changed to a mixture of B-LDPE and Petrosene 07C03C to produce Examples 8 to 18. Table 3 shows the mixing ratio of the mixture and the evaluation results.

実施例８～１８の発泡層と非発泡層について、実施例５を基準に、以下の通り外観を評価した。
発泡層（ラミネート後、発泡工程前）：実施例５と比較して、ポリエチレン樹脂層の厚みに斑がないかどうかを確認し、実施例５と同等以上の場合には“良好”とした。
発泡層（発泡工程後）：実施例５と比較して、発泡層が均一に発泡しているかどうか、凹凸が目立つかどうかを確認し、実施例５と同等以上の場合には“良好”とした。
非発泡層：実施例５と比較して、ポリエチレン樹脂層の厚みに斑がないかどうかを確認し、実施例５と同等以上の場合には“良好”とした。 The appearance of the foamed layer and the non-foamed layer of Examples 8 to 18 was evaluated as follows based on Example 5.
Foamed layer (after laminating, before foaming step): Compared with Example 5, it was confirmed whether the thickness of the polyethylene resin layer was uneven, and when it was equal to or higher than that of Example 5, it was regarded as “good”.
Foamed layer (after foaming step): Compared with Example 5, it was confirmed whether the foamed layer was uniformly foamed and whether unevenness was conspicuous, and when it was equal to or higher than that of Example 5, it was "good". did.
Non-foamed layer: Compared with Example 5, it was confirmed whether the thickness of the polyethylene resin layer was uneven, and when it was equal to or more than that of Example 5, it was regarded as “good”.

Figure 2022009813000004
Figure 2022009813000004

次に、実施例３におけるB-HDPE３を、B-HDPE３とペトロセンLW04-1との混合物に変更して、実施例１９～２９を製造した。混合物の配合比及び評価結果は表４の通りである。 Next, B-HDPE3 in Example 3 was changed to a mixture of B-HDPE3 and Petrosene LW04-1, and Examples 19 to 29 were produced. Table 4 shows the mixing ratio of the mixture and the evaluation results.

実施例１９～２９の発泡層と非発泡層について、実施例４を基準に、以下の通り外観を評価した。
発泡層（ラミネート後、発泡工程前）：実施例４と比較して、ポリエチレン樹脂層の厚みに斑がないかどうかを確認し、実施例４と同等以上の場合には“良好”とした。
発泡層（発泡工程後）：実施例４と比較して、発泡層が均一に発泡しているかどうか、凹凸が目立つかどうかを確認し、実施例４と同等以上の場合には“良好”とした。
非発泡層：実施例４と比較して、ポリエチレン樹脂層の厚みに斑がないかどうかを確認し、実施例４と同等以上の場合には“良好”とした。 The appearance of the foamed layer and the non-foamed layer of Examples 19 to 29 was evaluated as follows based on Example 4.
Foamed layer (after laminating, before foaming step): Compared with Example 4, it was confirmed whether the thickness of the polyethylene resin layer was uneven, and when it was equal to or higher than that of Example 4, it was evaluated as "good".
Foamed layer (after foaming step): Compared with Example 4, it was confirmed whether the foamed layer was uniformly foamed and whether the unevenness was conspicuous, and when it was equal to or higher than that of Example 4, it was "good". did.
Non-foamed layer: Compared with Example 4, it was confirmed whether the thickness of the polyethylene resin layer was uneven, and when it was equal to or more than that of Example 4, it was regarded as “good”.

Figure 2022009813000005
Figure 2022009813000005

さらに、実施例６におけるB-LDPEを、B-LDPEとペトロセン07C03Cとの混合物（配合比は実施例８～１８と同様）に変更して、発泡層及び非発泡層の外観を評価したが、実施例６と同様に良好だった。また、実施例６におけるB-HDPE３を、B-HDPE３とペトロセンLW04-1との混合物（配合比は実施例１９～２９と同様）に変更して、発泡層及び非発泡層の外観を評価したが、実施例６と同様に良好だった。 Further, the B-LDPE in Example 6 was changed to a mixture of B-LDPE and Petrosene 07C03C (the compounding ratio was the same as in Examples 8 to 18), and the appearances of the foamed layer and the non-foamed layer were evaluated. It was as good as in Example 6. Further, B-HDPE3 in Example 6 was changed to a mixture of B-HDPE3 and Petrosene LW04-1 (the compounding ratio was the same as in Examples 19 to 29), and the appearances of the foamed layer and the non-foamed layer were evaluated. However, it was as good as in Example 6.

以上の結果より、バイオマス由来のポリエチレン樹脂と化石燃料由来のポリエチレン樹脂を併用しても、ラミネート後の外観や発泡工程後の外観には差が無く、良好であることが確認できた。







































From the above results, it was confirmed that even if the polyethylene resin derived from biomass and the polyethylene resin derived from fossil fuel were used in combination, there was no difference in the appearance after laminating and the appearance after the foaming process, which was good.

１・・・紙基材
２・・・非発泡層（B-HDPE）
３・・・発泡層（B-LDPE）
１０・・紙基材
２１・・非発泡層１（ＰＥＴフィルム）
２２・・非発泡層２（ラミネート１：紙－PETフィルム間）
２３・・非発泡層３（ラミネート２：PETフィルム－B-HDPE間）
２４・・非発泡層４（B-HDPE）
２５・・アンカーコート層
３０・・発泡層（B-LDPE） 1 ... Paper base material 2 ... Non-foaming layer (B-HDPE)
3 ... Foam layer (B-LDPE)
10 ... Paper base material 21 ... Non-foaming layer 1 (PET film)
22 ... Non-foaming layer 2 (laminate 1: between paper and PET film)
23 ... Non-foaming layer 3 (Laminate 2: PET film-B-HDPE)
24 ... Non-foamed layer 4 (B-HDPE)
25 ... Anchor coat layer 30 ... Foam layer (B-LDPE)

Claims (1)

密度0.91g/cm3以上、0.93g/cm3未満の低密度ポリオレフィン樹脂からなる発泡層と、紙基材層と、密度0.943g/cm 3 以上、0.951g/cm 3 以下の中高密度ポリオレフィン樹脂からなる非発泡層とを順に備える積層体からなる発泡断熱容器であって、
前記低密度ポリオレフィン樹脂および／または前記中高密度ポリオレフィン樹脂は、バイオマスポリエチレン樹脂を含み、
前記中高密度ポリオレフィン樹脂は、低密度のバイオマスポリエチレン樹脂および高密度のバイオマスポリエチレン樹脂を混合して得られる樹脂である
ことを特徴とする発泡断熱容器。 A foam layer made of low-density polyolefin resin with a density of 0.91 g / cm 3 or more and less than 0.93 g / cm 3 , a paper substrate layer, and a medium-high density polyolefin resin with a density of 0.943 g / cm 3 or more and 0.951 g / cm 3 or less . A foamed heat insulating container made of a laminated body having a non-foamed layer made of the same material in order.
The low density polyolefin resin and / or the medium high density polyolefin resin contains a biomass polyethylene resin.
The medium-high-density polyolefin resin is a resin obtained by mixing a low-density biomass polyethylene resin and a high-density biomass polyethylene resin.
Effervescent insulation container characterized by that.
JP2021178655A 2019-11-06 2021-11-01 Laminate provided with resin layer derived from biomass and adiabatic container Pending JP2022009813A (en)

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JP7470468B1 (en) 2022-10-17 2024-04-18 シーピー化成株式会社 Laminated Sheets and Thermoformed Products

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JP6020975B2 (en) * 2015-10-27 2016-11-02 大日本印刷株式会社 Polyolefin resin film
WO2017150581A1 (en) * 2016-02-29 2017-09-08 日本ポリエチレン株式会社 Polyethylene-based resin composition for foamable laminated body, foamable laminated body, method for producing same, foam-processed paper, and heat insulation container
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JP6878838B2 (en) * 2016-11-02 2021-06-02 東ソー株式会社 Foaming laminate and foaming laminate
WO2019186640A1 (en) * 2018-03-26 2019-10-03 大日本印刷株式会社 Heat insulating container laminate, heat insulating container, method for manufacturing heat insulating container laminate, and method for manufacturing heat insulating container

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* Cited by examiner, † Cited by third party
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JP7470468B1 (en) 2022-10-17 2024-04-18 シーピー化成株式会社 Laminated Sheets and Thermoformed Products

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