JP5883308B2 - Thermoplastic multilayer resin sheet and molded container - Google Patents

Thermoplastic multilayer resin sheet and molded container Download PDF

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Publication number
JP5883308B2
JP5883308B2 JP2012028810A JP2012028810A JP5883308B2 JP 5883308 B2 JP5883308 B2 JP 5883308B2 JP 2012028810 A JP2012028810 A JP 2012028810A JP 2012028810 A JP2012028810 A JP 2012028810A JP 5883308 B2 JP5883308 B2 JP 5883308B2
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layer
resin sheet
resin
thermoplastic multilayer
strength
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JP2013163356A (en
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洪太 永岡
洪太 永岡
中里　利勝
利勝 中里
小茂田　含
含 小茂田
康次 中島
康次 中島
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Denka Co Ltd
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Denka Co Ltd
Denki Kagaku Kogyo KK
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Priority to JP2012028810A priority Critical patent/JP5883308B2/en
Priority to PCT/JP2013/053285 priority patent/WO2013122057A1/en
Priority to CN201380009101.9A priority patent/CN104114356B/en
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    • 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
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a general shape other than plane
    • 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
    • B32B27/065—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 foam
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • 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
    • 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
    • B65D75/00—Packages comprising articles or materials partially or wholly enclosed in strips, sheets, blanks, tubes, or webs of flexible sheet material, e.g. in folded wrappers
    • B65D75/28—Articles or materials wholly enclosed in composite wrappers, i.e. wrappers formed by associating or interconnecting two or more sheets or blanks
    • B65D75/30—Articles or materials enclosed between two opposed sheets or blanks having their margins united, e.g. by pressure-sensitive adhesive, crimping, heat-sealing, or welding
    • B65D75/32—Articles or materials enclosed between two opposed sheets or blanks having their margins united, e.g. by pressure-sensitive adhesive, crimping, heat-sealing, or welding one or both sheets or blanks being recessed to accommodate contents
    • B65D75/325—Articles or materials enclosed between two opposed sheets or blanks having their margins united, e.g. by pressure-sensitive adhesive, crimping, heat-sealing, or welding one or both sheets or blanks being recessed to accommodate contents one sheet being recessed, and the other being a flat not- rigid sheet, e.g. puncturable or peelable foil
    • B65D75/327—Articles or materials enclosed between two opposed sheets or blanks having their margins united, e.g. by pressure-sensitive adhesive, crimping, heat-sealing, or welding one or both sheets or blanks being recessed to accommodate contents one sheet being recessed, and the other being a flat not- rigid sheet, e.g. puncturable or peelable foil and forming several compartments
    • 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
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B32B2266/0221—Vinyl resin
    • B32B2266/0228—Aromatic vinyl resin, e.g. styrenic (co)polymers
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/718—Weight, e.g. weight per square meter
    • 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
    • B65D2575/00—Packages comprising articles or materials partially or wholly enclosed in strips, sheets, blanks, tubes or webs of flexible sheet material, e.g. in folded wrappers
    • B65D2575/28—Articles or materials wholly enclosed in composite wrappers, i.e. wrappers formed by association or interconnecting two or more sheets or blanks
    • B65D2575/30—Articles or materials enclosed between two opposed sheets or blanks having their margins united, e.g. by pressure-sensitive adhesive, crimping, heat-sealing, or welding
    • B65D2575/32—Articles or materials enclosed between two opposed sheets or blanks having their margins united, e.g. by pressure-sensitive adhesive, crimping, heat-sealing, or welding one or both sheets or blanks being recessed to accommodate contents
    • B65D2575/3209—Details
    • B65D2575/3281—Tear lines dividing the package into a plurality of packages

Description

本発明は、熱可塑性多層樹脂シート及びそれを成形してなる成形容器に関する。   The present invention relates to a thermoplastic multilayer resin sheet and a molded container formed by molding the same.

従来から、ヨーグルトやミルクポーションをはじめとする乳製品の容器には、成形性に優れたスチレン系樹脂が用いられてきた。近年では、酸素に対するガスバリア性、防湿性などの特性を各層に持たせた多層構造のスチレン系発泡シートが開発されている（特許文献１参照）。   Conventionally, styrenic resins having excellent moldability have been used in containers for dairy products such as yogurt and milk portions. In recent years, a styrene foam sheet having a multilayer structure in which each layer has characteristics such as a gas barrier property against oxygen and moisture resistance has been developed (see Patent Document 1).

更に、近年では環境負荷低減の為、廃棄物を削減しようとする社会的動向があり、これに伴い、シート内部に発泡層を配することで軽量化を図ろうとする技術が考案されている（特許文献２参照）。   Furthermore, in recent years, there has been a social trend to reduce waste to reduce the environmental load, and in accordance with this, a technology has been devised to reduce the weight by arranging a foam layer inside the sheet ( Patent Document 2).

上記従来の容器では、その内部に発泡層を設けることにより、１５〜２０％の軽量化が可能であるが、一方で発泡層を持たないシートと比較して容器落下強度が大きく低下するという問題を抱えている。また、一方の面側からノッチが形成される樹脂シートの場合、熱成形後のノッチ折れ性が不十分であるという問題があった。   In the above conventional container, it is possible to reduce the weight by 15 to 20% by providing a foam layer therein, but on the other hand, the problem that the container drop strength is greatly reduced compared to a sheet having no foam layer. Have Moreover, in the case of the resin sheet in which a notch is formed from one surface side, there is a problem that the notch folding property after thermoforming is insufficient.

特開２０１１−５１２６４号公報JP 2011-51264 A 特表２００３−５２２０５２号公報Japanese translation of PCT publication No. 2003-522052

本発明は、上記事情に鑑みてなされたもので、従来の発泡シートでは困難であった軽量化と強度維持の両立という課題を解決し、軽量性と強度を具備する上、熱成形後のノッチ折れ性を十分なものとできる熱可塑性多層樹脂シートを提供することを目的とする。またこのような熱可塑性多層樹脂シートを用いて製造される成形容器を提供することも目的とする。   The present invention has been made in view of the above circumstances, and solves the problem of achieving both weight reduction and strength maintenance, which has been difficult with conventional foamed sheets, and has not only light weight and strength but also a notch after thermoforming. An object of the present invention is to provide a thermoplastic multilayer resin sheet that can have sufficient foldability. It is another object of the present invention to provide a molded container manufactured using such a thermoplastic multilayer resin sheet.

本発明者は、発泡層を挟んで両面にソリッド層が形成され、一方の面側からノッチが形成される熱可塑性多層樹脂シートにおいて、ノッチ形成面を構成するソリッド層と発泡層との間に強度維持層を設けることで、前記課題を解決できることを見出し、本発明を完成するに至ったものである。   In the thermoplastic multilayer resin sheet in which a solid layer is formed on both sides with a foam layer sandwiched and a notch is formed from one surface side, the inventor is between the solid layer and the foam layer constituting the notch formation surface. It has been found that the above-mentioned problems can be solved by providing a strength maintaining layer, and the present invention has been completed.

すなわち、本発明の主たる態様によれば、発泡層を挟んで両面にソリッド層が形成され、一方の面側からノッチが形成される熱可塑性多層樹脂シートであって、ノッチ形成面を構成するソリッド層と発泡層との間に、ポリオレフィン系樹脂により形成された強度維持層が設けられ、前記発泡層を境に前記強度維持層を含むノッチ形成面側の厚みが、総厚みの２５％以下である熱可塑性多層樹脂シートが提供される。   That is, according to the main aspect of the present invention, a thermoplastic multilayer resin sheet in which a solid layer is formed on both sides of a foam layer and a notch is formed from one surface side, the solid constituting the notch forming surface A strength maintaining layer formed of a polyolefin-based resin is provided between the layer and the foamed layer, and the thickness on the notch forming surface side including the strength maintaining layer with the foamed layer as a boundary is 25% or less of the total thickness A thermoplastic multilayer resin sheet is provided.

上記において、発泡層は、発泡倍率が１．３〜２．０倍であるものが好ましい。シートの総厚みは通常は６００〜１２００μｍの範囲とされる。前記強度維持層の厚みは例えば２０〜６０μｍの範囲とできる。
また、前記発泡層及び前記ソリッド層は何れもポリスチレン系樹脂により形成されるのが好ましく、また前記強度維持層と該強度維持層に隣接する層との間には更に接着層を介在させてもよい。 In the above, the foamed layer preferably has a foaming ratio of 1.3 to 2.0 times. The total thickness of the sheet is usually in the range of 600 to 1200 μm. The strength maintaining layer can have a thickness in the range of, for example, 20 to 60 μm.
The foam layer and the solid layer are preferably formed of polystyrene resin, and an adhesive layer may be further interposed between the strength maintaining layer and the layer adjacent to the strength maintaining layer. Good.

また本発明の別の態様によれば、本発明に係る熱可塑性多層樹脂シートを熱成形してなる成形容器が提供される。   According to another aspect of the present invention, there is provided a molded container formed by thermoforming the thermoplastic multilayer resin sheet according to the present invention.

本発明の熱可塑性多層樹脂シートは、軽量性、強度を具備すると共に、熱成形後のノッチ折れ性を十分なものとすることが容易である。また、本発明の成形容器は、軽量性、落下強度を具備すると共に、ノッチ折れ性にも優れる。   The thermoplastic multilayer resin sheet of the present invention has light weight and strength, and it is easy to make the notch bendability after thermoforming sufficient. In addition, the molded container of the present invention has light weight and drop strength, and is excellent in notch foldability.

本発明の熱可塑性多層樹脂シートの巻き姿を示す概略斜視図であり、該シートの一部の断面を示す概略断面図も併せて示す。It is a schematic perspective view which shows the winding form of the thermoplastic multilayer resin sheet of this invention, and also shows the schematic sectional drawing which shows the cross section of a part of this sheet | seat. 本発明の成形容器の一例を示す概略斜視図である。It is a schematic perspective view which shows an example of the shaping | molding container of this invention. 図２の成形容器の概略側面図である。It is a schematic side view of the shaping | molding container of FIG. 容器の打ち抜き工程を説明するための概略図である。It is the schematic for demonstrating the punching process of a container.

図１中の断面図は、本発明の一実施形態に係る熱可塑性多層樹脂シートの断面を示すもので、ノッチが形成されることとなる面を構成するソリッド層を最上層とし、下方に向けて順に、接着層、強度維持層、接着層、発泡層、ソリッド層を有する積層構造とされている。以下、発泡層、ソリッド層、強度維持層、接着層の順に各層を説明する。   The cross-sectional view in FIG. 1 shows a cross section of a thermoplastic multilayer resin sheet according to an embodiment of the present invention. The solid layer constituting the surface on which the notch is to be formed is the uppermost layer and is directed downward. The laminated structure has an adhesive layer, a strength maintaining layer, an adhesive layer, a foamed layer, and a solid layer. Hereinafter, each layer will be described in the order of a foam layer, a solid layer, a strength maintaining layer, and an adhesive layer.

＜発泡層＞
前記発泡層は、本発明の分野で使用できる発泡層を形成できるものであれば、如何なる樹脂で形成してもよいが、本発明の一実施形態では、スチレン系樹脂で形成される。使用されるスチレン系樹脂としては、スチレン、α−メチルスチレン、ｐ−メチルスチレン、ジメチルスチレン、ｐ−ｔ−ブチルスチレン、クロロスチレン等のスチレン系モノマーの単独又は共重合体、それらスチレン系モノマーと他のモノマーとの共重合体、例えばスチレン−アクリルニトリル共重合体（ＡＳ樹脂）、あるいは前記スチレン系モノマーと更に他のポリマー、例えば、ポリブタジエン、スチレン−ブタジエン共重合体、ポリイソプレン、ポリクロロプレン等のジエン系ゴム質重合体の存在下にグラフト重合したグラフト共重合体、例えばハイインパクトポリスチレン（ＨＩＰＳ樹脂）、スチレン−アクリルニトリルグラフト共重合体（ＡＢＳ樹脂）等が挙げられる。 <Foamed layer>
The foamed layer may be formed of any resin as long as it can form a foamed layer that can be used in the field of the present invention. In one embodiment of the present invention, the foamed layer is formed of a styrene resin. Styrene resins used include styrene monomers such as styrene, α-methyl styrene, p-methyl styrene, dimethyl styrene, pt-butyl styrene, chlorostyrene, or copolymers, and styrene monomers. Copolymers with other monomers, such as styrene-acrylonitrile copolymer (AS resin), or other polymers with the styrene monomer, such as polybutadiene, styrene-butadiene copolymer, polyisoprene, polychloroprene, etc. Examples thereof include graft copolymers obtained by graft polymerization in the presence of a diene rubber polymer such as high impact polystyrene (HIPS resin), styrene-acrylonitrile graft copolymer (ABS resin), and the like.

なかでも汎用ポリスチレン（ＧＰＰＳ樹脂）、ハイインパクトポリスチレン（ＨＩＰＳ樹脂）が成形容器の剛性、成形性の観点から好ましい。   Of these, general-purpose polystyrene (GPPS resin) and high-impact polystyrene (HIPS resin) are preferred from the viewpoint of the rigidity and moldability of the molded container.

スチレン系樹脂は、ブタジエンゴム成分を４〜８質量％含有することが好ましい。ブタジエンゴム成分含有量は、ＧＰＰＳとＨＩＰＳのブレンドにより調整するのが簡便な方法であるが、ＨＩＰＳの製造段階で調整しても構わない。ブタジエンゴム成分が４質量％未満であると実用上十分な容器強度が得られなくなる可能性があり、８質量％を超えると、熱成形時に熱盤付着等の不具合を起こす可能性がある。   The styrene resin preferably contains 4 to 8% by mass of a butadiene rubber component. The butadiene rubber component content is a simple method of adjusting by blending GPPS and HIPS, but it may be adjusted at the manufacturing stage of HIPS. If the butadiene rubber component is less than 4% by mass, a practically sufficient container strength may not be obtained. If it exceeds 8% by mass, problems such as adhesion of a hot platen may occur during thermoforming.

スチレン系樹脂には、必要に応じて、本発明の効果を阻害しない範囲で、顔料、染料などの着色剤、シリコンオイルやアルキルエステル系等の離型剤、ガラス繊維等の繊維状強化剤、タルク、クレイ、シリカなどの粒状滑剤、スルホン酸とアルカリ金属などとの塩化合物やポリアルキレングリコール等の帯電防止剤及び紫外線吸収剤、抗菌剤のような添加剤を添加することができる。また、本発明の熱可塑性多層樹脂シートや成形容器の製造工程で発生したスクラップ樹脂を混合して用いることもできる。   In the styrene resin, if necessary, a colorant such as a pigment or a dye, a release agent such as silicone oil or alkyl ester, a fibrous reinforcing agent such as glass fiber, etc. Additives such as particulate lubricants such as talc, clay and silica, salt compounds of sulfonic acid and alkali metals, antistatic agents such as polyalkylene glycol, ultraviolet absorbers and antibacterial agents can be added. In addition, the thermoplastic multilayer resin sheet of the present invention and the scrap resin generated in the manufacturing process of the molded container can be mixed and used.

発泡層に添加する発泡剤としては、種々の揮発性発泡剤や分解型発泡剤がある。揮発性発泡剤としては、例えば、炭化水素、プロパン、ｉ−ブタン、ｎ−ブタン、ｉ−ペンタン、ｎ−ペンタン、あるいはこれらの混合物、そして、Ｎ２、ＣＯ２、Ｎ２／ＣＯ２、水などが挙げられる。 Examples of the foaming agent added to the foamed layer include various volatile foaming agents and decomposable foaming agents. Volatile blowing agents include, for example, hydrocarbons, propane, i-butane, n-butane, i-pentane, n-pentane, or mixtures thereof, and N 2 , CO 2 , N 2 / CO 2 , water Etc.

分解型発泡剤として、例えば、アゾジカルボン酸アミド、ジニトロペンタメチレンテトラミン、４、４’−オキシビス（ベンゼンスルホニルヒドラジド）などを挙げることができる。さらに、重炭酸ナトリウムや、クエン酸などの有機酸もしくはその塩と重炭酸塩との組み合わせなども使用することができる。また、例えば重炭酸ナトリウムや、クエン酸などの有機酸もしくはその塩と重炭酸塩との組み合わせは、低分子オレフィン化合物、流動パラフィン、牛脂油などでコーティングしても使用することができる。その他、これらの混合物を使用することも可能で、これらを２種類以上混合してもよい。これらはいずれも粉末、フレーク、又は熱可塑性樹脂とのマスターバッチとして入手することもできる。特に、ポリオレフィンをポリスチレンに混合して分解型発泡剤を使用すると、該ポリオレフィンは気泡調整剤としての効果がある。また、分解型発泡剤とＮ２、ＣＯ２、ｉ−ブタン、ｎ−ブタン、ｉ−ペンタン、ｎ−ペンタンとを併用すると気泡が細かく、かつ成形性がよい。 Examples of the decomposable foaming agent include azodicarboxylic acid amide, dinitropentamethylenetetramine, 4,4′-oxybis (benzenesulfonylhydrazide), and the like. Further, sodium bicarbonate, an organic acid such as citric acid or a combination thereof and a bicarbonate can be used. In addition, for example, sodium bicarbonate, an organic acid such as citric acid or a combination of a salt thereof and a bicarbonate can be used even when coated with a low molecular weight olefin compound, liquid paraffin, beef tallow oil, or the like. In addition, these mixtures can also be used, and two or more of these may be mixed. All of these can also be obtained as a masterbatch with powder, flakes, or a thermoplastic resin. In particular, when a decomposable foaming agent is used by mixing polyolefin with polystyrene, the polyolefin has an effect as a cell regulator. Further, when a decomposable foaming agent is used in combination with N 2 , CO 2 , i-butane, n-butane, i-pentane, and n-pentane, the bubbles are fine and the moldability is good.

発泡層の厚みとしては好ましくは３００〜７００μｍ、より好ましくは３５０〜５００μｍがよい。３００μｍ未満であると十分な軽量性が得られない可能性があり、７００μｍを超えると、成形容器の強度が低下し、深絞り成形には適さない。   The thickness of the foam layer is preferably 300 to 700 μm, more preferably 350 to 500 μm. If it is less than 300 μm, there is a possibility that sufficient lightness cannot be obtained. If it exceeds 700 μm, the strength of the molded container is lowered and it is not suitable for deep drawing.

本発明においては、発泡層の発泡倍率としては、好ましくは１．３〜２．０倍、より好ましくは１．４〜１．８倍である。１．３倍未満であると、シートについて十分な軽量性が得られず、２．０倍以上であると、成形容器の強度が低下し、深絞り成形には適さない。   In the present invention, the expansion ratio of the foam layer is preferably 1.3 to 2.0 times, more preferably 1.4 to 1.8 times. If it is less than 1.3 times, sufficient lightness cannot be obtained for the sheet, and if it is 2.0 times or more, the strength of the molded container is lowered and it is not suitable for deep drawing.

＜ソリッド層＞
ソリッド層は非発泡層であり、発泡層に用いられる樹脂と同一又は類似の樹脂によって形成されるのが好ましい。よって、本発明の好適な実施形態では、ソリッド層は、スチレン系樹脂により形成される。ソリッド層を構成するスチレン系樹脂としては、スチレン、α−メチルスチレン、ｐ−メチルスチレン、ジメチルスチレン、ｐ−ｔ−ブチルスチレン、クロロスチレン等のスチレン系モノマーの単独又は共重合体、それらスチレン系モノマーと他のモノマーとの共重合体、例えばスチレン−アクリルニトリル共重合体（ＡＳ樹脂）、又は前記スチレン系モノマーと更に他のポリマー、例えば、ポリブタジエン、スチレン−ブタジエン共重合体、ポリイソプレン、ポリクロロプレン等のジエン系ゴム質重合体の存在下にグラフト重合したグラフト共重合体、例えばハイインパクトポリスチレン（ＨＩＰＳ樹脂）、スチレン−アクリルニトリルグラフト共重合体（ＡＢＳ樹脂）等が挙げられる。 <Solid layer>
The solid layer is a non-foamed layer, and is preferably formed of the same or similar resin as that used for the foamed layer. Therefore, in a preferred embodiment of the present invention, the solid layer is formed of a styrenic resin. As the styrene resin constituting the solid layer, styrene monomers such as styrene, α-methyl styrene, p-methyl styrene, dimethyl styrene, pt-butyl styrene, chlorostyrene, or the like, copolymers thereof Copolymer of monomer and other monomer, such as styrene-acrylonitrile copolymer (AS resin), or other polymer such as styrene-based monomer, such as polybutadiene, styrene-butadiene copolymer, polyisoprene, poly Examples thereof include a graft copolymer obtained by graft polymerization in the presence of a diene rubber polymer such as chloroprene, such as high impact polystyrene (HIPS resin), styrene-acrylonitrile graft copolymer (ABS resin), and the like.

なかでも汎用ポリスチレン（ＧＰＰＳ樹脂）、ハイインパクトポリスチレン（ＨＩＰＳ樹脂）が成形容器の剛性、成形性の観点から好ましい。   Of these, general-purpose polystyrene (GPPS resin) and high-impact polystyrene (HIPS resin) are preferred from the viewpoint of the rigidity and moldability of the molded container.

スチレン系樹脂は、ブタジエンゴム成分を４〜８質量％含有することが好ましい。ブタジエンゴム成分含有量は、ＧＰＰＳ樹脂とＨＩＰＳ樹脂のブレンドにより調整するのが簡便な方法であるが、ＨＩＰＳ樹脂の製造段階で調整しても構わない。４質量％未満であると実用上十分な容器強度が得られなくなる可能性があり、８質量％を超えると、熱成形時に溶融樹脂の熱盤への付着等の不具合を起こす可能性がある。   The styrene resin preferably contains 4 to 8% by mass of a butadiene rubber component. The butadiene rubber component content is a simple method to adjust by blending GPPS resin and HIPS resin, but it may be adjusted at the manufacturing stage of HIPS resin. If the amount is less than 4% by mass, a practically sufficient container strength may not be obtained. If the amount exceeds 8% by mass, problems such as adhesion of the molten resin to the hot platen may occur during thermoforming.

スチレン系樹脂には、必要に応じて、本発明の効果を阻害しない範囲で、顔料、染料などの着色剤、シリコンオイルやアルキルエステル系等の離型剤、ガラス繊維等の繊維状強化剤、タルク、クレイ、シリカなどの粒状滑剤、スルホン酸とアルカリ金属などとの塩化合物やポリアルキレングリコール等の帯電防止剤及び紫外線吸収剤、抗菌剤のような添加剤を添加することができる。また、本発明の熱可塑性多層樹脂シートやそれを熱成形して成る成形容器の製造工程で発生したスクラップ樹脂を混合して用いることもできる。   In the styrene resin, if necessary, a colorant such as a pigment or a dye, a release agent such as silicone oil or alkyl ester, a fibrous reinforcing agent such as glass fiber, etc. Additives such as particulate lubricants such as talc, clay and silica, salt compounds of sulfonic acid and alkali metals, antistatic agents such as polyalkylene glycol, ultraviolet absorbers and antibacterial agents can be added. In addition, the thermoplastic multilayer resin sheet of the present invention and the scrap resin generated in the manufacturing process of the molded container formed by thermoforming it can be mixed and used.

ノッチが形成される面側のソリッド層の厚みとしては、好ましくは３０〜２６０μｍ、より好ましくは５０〜１５０μｍである。３０μｍ未満であると、熱成形を経て引き伸ばされる際にソリッド層が切れて強度維持層が剥き出しになり、容器表面の印字適性が損なわれる可能性がある。また、２６０μｍを超えると、ノッチを形成する際の刃の挿入深さを大きくする必要があり、容器形状の保持性能及び容器強度が低下する恐れがある。   The thickness of the solid layer on the surface side where the notch is formed is preferably 30 to 260 μm, more preferably 50 to 150 μm. If the thickness is less than 30 μm, the solid layer is cut when it is stretched through thermoforming, and the strength maintaining layer is exposed, which may impair the printability of the container surface. Moreover, when it exceeds 260 micrometers, it is necessary to enlarge the insertion depth of the blade at the time of forming a notch, and there exists a possibility that the holding | maintenance performance and container strength of a container shape may fall.

ノッチが形成されない面側のソリッド層の厚みとしては、好ましくは１４０〜５１０μｍ、より好ましくは１７０〜３９０μｍである。１４０μｍ未満であると、熱成形して得られた容器の剛性が不十分となる可能性があり、５１０μｍを超えると、ノッチを形成した後のノッチ折れ性が低下する可能性がある。   The thickness of the solid layer on the side where no notch is formed is preferably 140 to 510 μm, more preferably 170 to 390 μm. If it is less than 140 μm, the rigidity of the container obtained by thermoforming may be insufficient, and if it exceeds 510 μm, the notch breakability after forming the notch may be lowered.

＜強度維持層＞
強度維持層は、強度を付与するために設ける靱性に優れた層で、本発明の一実施形態では、ポリオレフィン系樹脂により形成される。かかるポリオレフィン系樹脂としては、例えば、低密度ポリエチレン、中密度ポリエチレン、高密度ポリエチレン、直鎖状（線状）ポリエチレン、メタロセン触媒を使用して重合したエチレン−α・オレフィン共重合体、ポリプロピレン、エチレン−酢酸ビニル共重合体、アイオノマー樹脂、エチレン−アクリル酸共重合体、エチレン−アクリル酸エチル共重合体、エチレン−メタクリル酸共重合体、エチレン−メタクリル酸メチル共重合体、エチレン−プロピレン共重合体、メチルペンテンポリマー、ポリブテンポリマー、ポリエチレン又はポリプロピレン等のポリオレフィン系樹脂をアクリル酸、メタクリル酸、マレイン酸、無水マレイン酸、フマール酸、イタコン酸等の不飽和カルボン酸で変性した酸変性ポリオレフィン樹脂、ポリ酢酸ビニル系樹脂、ポリ（メタ）アクリル系樹脂、ポリ塩化ビニル系樹脂、その他の樹脂を使用することができる。 <Strength maintenance layer>
The strength maintaining layer is a layer having excellent toughness provided for imparting strength, and is formed of a polyolefin-based resin in one embodiment of the present invention. Examples of such polyolefin resins include low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) polyethylene, ethylene-α / olefin copolymer polymerized using a metallocene catalyst, polypropylene, ethylene -Vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer Polyolefin resins such as methylpentene polymer, polybutene polymer, polyethylene or polypropylene modified with unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, vinegar It may be used vinyl-based resins, poly (meth) acrylic resins, polyvinyl chloride resins, other resins.

また、強度維持層を構成するポリオレフィン系樹脂としては、ノッチなし試験片のアイゾット衝撃強さが１００ｋＪ／ｍ２以上である樹脂が特に好ましい。１００ｋＪ／ｍ２未満の樹脂では靭性が不十分となり、樹脂シート及びそれを熱成形してなる成形容器の強度が低下してしまう場合がありうる。 Further, as the polyolefin-based resin constituting the strength maintaining layer, a resin having an Izod impact strength of a notched test piece of 100 kJ / m 2 or more is particularly preferable. If the resin is less than 100 kJ / m 2 , the toughness may be insufficient, and the strength of the resin sheet and a molded container formed by thermoforming the resin sheet may decrease.

ここで、ノッチなし試験片のアイゾット衝撃強さとは、ノッチなし試験片の破壊時に吸収される衝撃エネルギーを試験片の初めの断面積で除した値で表わされ、ＪＩＳ Ｋ７１１０に記載されている手法に従って評価される。以下に試験法の概要を記しておく。
（ノッチなし試験片のアイゾット衝撃強さの評価法）
・試験片： 試験片は、ＩＳＯ ２８１８の規定に従ってシートから切削加工する。
（推奨される試験片の形状と寸法）
長さ ｌ＝８０ｍｍ±２ｍｍ
幅 ｂ＝１０．０ｍｍ±０．２ｍｍ
厚さ ｈ＝４．０ｍｍ±０．２ｍｍ
・装置： 試験機は、振り子式衝撃試験機で、堅固な構造とし、試験片の破壊時に吸収される衝撃エネルギー（Ｗ）を測定できるものとする。
・試験手順及び結果の表示： 試験は少なくとも１０個の試験片について行う。ノッチなし試験片のアイゾット衝撃強さＡｉｕは次式で算出し、計算した平均値は有効数字２桁で報告する。
Ａｉｕ＝Ｗ／ｈｂ×１０３（ｋＪ／ｍ２）
Ｗ：試験片に吸収された補正後の衝撃エネルギー（Ｊ）
ｈ：試験片の厚さ（ｍｍ）
ｂ：試験片の幅（ｍｍ） Here, the Izod impact strength of the unnotched specimen is expressed by a value obtained by dividing the impact energy absorbed when the unnotched specimen is broken by the initial cross-sectional area of the specimen, and is described in JIS K7110. It is evaluated according to the method. The outline of the test method is described below.
(Evaluation method of Izod impact strength of unnotched specimens)
Test piece: The test piece is cut from the sheet in accordance with ISO 2818.
(Recommended specimen shape and dimensions)
Length l = 80mm ± 2mm
Width b = 10.0mm ± 0.2mm
Thickness h = 4.0mm ± 0.2mm
-Equipment: The tester shall be a pendulum impact tester with a solid structure and capable of measuring impact energy (W) absorbed when the specimen is destroyed.
Test procedure and result display: The test is performed on at least 10 test pieces. The Izod impact strength A iu of the unnotched specimen is calculated by the following formula, and the calculated average value is reported by two significant figures.
A iu = W / hb × 10 3 (kJ / m 2 )
W: Impact energy after correction absorbed by the specimen (J)
h: Test piece thickness (mm)
b: Width of test piece (mm)

強度維持層の厚みとしては、好ましくは２０〜６０μｍ、より好ましくは３０〜５０μｍがよい。２０μｍ未満であるとシート及び成形容器に十分な強度を付与できない可能性があり、６０μｍを超えるとノッチ形成時、強度維持層が切断されずノッチ折れ性が悪くなる恐れがある。   The thickness of the strength maintaining layer is preferably 20 to 60 μm, more preferably 30 to 50 μm. If the thickness is less than 20 μm, there is a possibility that sufficient strength cannot be imparted to the sheet and the molded container. If the thickness exceeds 60 μm, the strength maintaining layer may not be cut during notch formation, and the notch breakability may be deteriorated.

＜接着層＞
接着層は、任意の層で、本発明の分野で使用でき、隣接層を接着する接着性を具備するものであれば如何なる樹脂で形成してもよいが、本発明の一実施形態では、変性ポリオレフィン系樹脂が使用される。かかる変性ポリオレフィン系樹脂としては、エチレン、プロピレン、ブテン−１等の炭素数２〜８程度のオレフィンの単独重合体、それらのオレフィンとエチレン、プロピレン、ブテン−１、３−メチルブテン−１、ペンテン−１、４−メチルペンテン−１、ヘキセン−１、オクテン−１、デセン−１等の炭素数２〜２０程度の他のオレフィンや酢酸ビニル、塩化ビニル、アクリル酸、メタクリル酸、アクリル酸エステル、メタクリル酸エステル、スチレン等のビニル化合物との共重合体等のオレフィン系樹脂や、エチレン−プロピレン共重合体、エチレン−プロピレン−ジエン共重合体、エチレン−ブテン−１共重合体、プロピレン−ブテン−１共重合体等の共重合体ゴムを、アクリル酸、メタクリル酸、クロトン酸、イソクロトン酸、マレイン酸、フマール酸、イタコン酸、シトラコン酸、テトラヒドロフタル酸等の不飽和カルボン酸、又はその酸ハライド、アミド、イミド、無水物、エステル等の誘導体、具体的には、塩化マレニル、マレイミド、無水マレイン酸、無水シトラコン酸、マレイン酸モノメチル、マレイン酸ジメチル、マレイン酸グリシジル等でグラフト反応条件下に変性したものが代表的なものとして挙げられる。 <Adhesive layer>
The adhesive layer is an arbitrary layer and can be used in the field of the present invention, and may be formed of any resin as long as it has adhesiveness to bond adjacent layers. A polyolefin resin is used. Examples of such modified polyolefin resins include homopolymers of olefins having about 2 to 8 carbon atoms such as ethylene, propylene and butene-1, and these olefins and ethylene, propylene, butene-1, 3-methylbutene-1, pentene- Other olefins having about 2 to 20 carbon atoms such as 1,4-methylpentene-1, hexene-1, octene-1 and decene-1, vinyl acetate, vinyl chloride, acrylic acid, methacrylic acid, acrylic ester, methacrylic acid Olefin resins such as acid esters and copolymers with vinyl compounds such as styrene, ethylene-propylene copolymers, ethylene-propylene-diene copolymers, ethylene-butene-1 copolymers, propylene-butene-1 Copolymer rubbers such as copolymers can be used with acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, Unsaturated carboxylic acids such as inic acid, fumaric acid, itaconic acid, citraconic acid and tetrahydrophthalic acid, or derivatives thereof such as acid halides, amides, imides, anhydrides and esters, specifically, maleyl chloride, maleimide, anhydrous Typical examples include those modified with maleic acid, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate and the like under the graft reaction conditions.

なかでも、不飽和ジカルボン酸又はその無水物、特にマレイン酸又はその無水物で変性したエチレン系樹脂、プロピレン系樹脂、又はエチレン−プロピレン又はブテン−１共重合体ゴムが好適である。   Among them, an ethylene-based resin, a propylene-based resin, or an ethylene-propylene or butene-1 copolymer rubber modified with an unsaturated dicarboxylic acid or an anhydride thereof, particularly maleic acid or an anhydride thereof is preferable.

接着層の厚みとしては、好ましくは３〜１０μｍ、より好ましくは４〜６μｍがよい。３μｍ未満であると、十分な層間接着強度が得られなくなる可能性があり、１０μｍを超えると、熱成形の打ち抜き時に樹脂ヒゲが発生したり、ノッチ折れ性が不十分となる可能性がある。   The thickness of the adhesive layer is preferably 3 to 10 μm, more preferably 4 to 6 μm. If the thickness is less than 3 μm, sufficient interlayer adhesion strength may not be obtained. If the thickness exceeds 10 μm, resin whiskering may occur at the time of thermoforming punching, or notch breakability may be insufficient.

＜熱可塑性多層樹脂シート＞
本発明の熱可塑性多層樹脂シートの層構成は、図１の実施形態に示すように、基本的に、ソリッド層／接着層／強度維持層／接着層／発泡層／ソリッド層であるが、層構成はこれに限定されるものではない。例えば、本発明の熱可塑性多層樹脂シートやそれを熱成形して成る成形容器の製造工程で発生したスクラップ樹脂の屑等からなる層を、ノッチが形成される反対側に積層してもよい。 <Thermoplastic multilayer resin sheet>
The layer structure of the thermoplastic multilayer resin sheet of the present invention is basically solid layer / adhesive layer / strength maintaining layer / adhesive layer / foamed layer / solid layer as shown in the embodiment of FIG. The configuration is not limited to this. For example, you may laminate | stack the layer which consists of scraps of scrap resin etc. which generate | occur | produced in the manufacturing process of the thermoplastic multilayer resin sheet of this invention and the molding container formed by thermoforming it on the opposite side in which a notch is formed.

熱可塑性多層シートの総厚みとしては、好ましくは６００〜１２００μｍ、より好ましくは７００〜９００μｍである。６００μｍ未満であると、熱成形して得られた容器の強度が不十分となる可能性があり、１２００μｍを超えると容器の製造コストが高くなる可能性がある。また、熱成形後の成形容器のノッチ折れ性は、形成されるノッチの深さ等に応じて変動しうるが、種々の構成の多層シートを製造し、種々のノッチ形成条件下でノッチを形成してその折れ性を試験した結果、成形容器のノッチ折れ性を十分なものとするためには、発泡層を境に強度維持層を含むノッチ形成面側の厚みを、総厚みの２５％以下としておくべきであることを知見した。よって、本実施形態においては、発泡層を境に強度維持層を含むノッチ形成面側の厚み（図１に示されるように、ノッチ形成面側のソリッド層／接着層／強度維持層／接着層までの厚み）が、上述の総厚みの２５％以下でなければならない。   The total thickness of the thermoplastic multilayer sheet is preferably 600 to 1200 μm, more preferably 700 to 900 μm. If it is less than 600 μm, the strength of the container obtained by thermoforming may be insufficient, and if it exceeds 1200 μm, the production cost of the container may increase. In addition, the notch foldability of the molded container after thermoforming may vary depending on the depth of the notch to be formed, etc., but it is possible to manufacture multilayer sheets with various configurations and form notches under various notch forming conditions. As a result of testing the bendability, in order to make the notch bendability of the molded container sufficient, the thickness on the notch forming surface side including the strength maintaining layer with the foam layer as a boundary is 25% or less of the total thickness. I found out that it should be. Therefore, in the present embodiment, the thickness on the notch forming surface side including the strength maintaining layer with the foam layer as a boundary (as shown in FIG. 1, the solid layer / adhesive layer / strength maintaining layer / adhesive layer on the notch forming surface side) Up to 25% of the total thickness described above.

熱可塑性多層樹脂シートの成形方法は、特に限定されず一般的な方法を用いることができる。例えば、４台もしくはそれ以上の単軸押出機を用いて各々の原料樹脂を溶融押出し、フィードブロックとＴダイによって多層樹脂シートを得る方法や、マルチマニホールドダイを使用して多層樹脂シートを得る方法が挙げられる。   A method for forming the thermoplastic multilayer resin sheet is not particularly limited, and a general method can be used. For example, each raw resin is melt-extruded using four or more single-screw extruders, and a multilayer resin sheet is obtained using a feed block and a T die, or a multilayer resin sheet is obtained using a multi-manifold die Is mentioned.

＜成形容器＞
図２に、本発明の成形容器の一例を示す。
本発明の成形容器は、上記本発明の熱可塑性多層樹脂シートを成形してなる。熱成形方法としては、一般的な真空成形、圧空成形やこれらの応用として、シートの片面にプラグを接触させて成形を行うプラグアシスト法、またシートの両面に一対をなす雄雌型を接触させて成形を行う、いわゆるマッチモールド成形と称される方法等が挙げられるが、これに限定されるものではない。また、成形前にシートを加熱軟化させる方法として非接触加熱である赤外線ヒーター等による輻射加熱等、公知のシート加熱方法を適用することができる。 <Molded container>
FIG. 2 shows an example of the molded container of the present invention.
The molded container of the present invention is formed by molding the thermoplastic multilayer resin sheet of the present invention. Thermoforming methods include general vacuum forming, pressure forming, and as an application of these, the plug assist method in which a plug is brought into contact with one side of the sheet to form, and a pair of male and female dies are brought into contact with both sides of the sheet. A method called so-called “match mold molding” is performed, but the method is not limited to this. Further, as a method for heating and softening the sheet before molding, a known sheet heating method such as radiant heating with an infrared heater or the like which is non-contact heating can be applied.

また、本発明の成形容器はノッチを有する。ノッチは断面Ｖ字形状であり、一方の面側、すなわち発泡層を境に強度維持層を含む側に、熱盤方式等により加熱してＶ字形状の刃を挿入することにより形成することができる。   The molded container of the present invention has a notch. The notch has a V-shaped cross section, and can be formed by inserting a V-shaped blade by heating on one surface side, that is, the side including the strength maintaining layer with the foam layer as a boundary, by a hot plate method or the like. it can.

以下、実施例及び比較例を挙げて本発明をより具体的に説明するが、本発明は実施例等の内容に何ら限定されるものではない。   EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to the content of an Example etc. at all.

実施例で用いた樹脂原料は以下の通りである。
（１）強度維持層
・アイゾット衝撃強さ（ノッチ無）が１００ｋＪ／ｍ２以上のポリオレフィン系樹脂として、低密度ポリエチレン樹脂「ノバテックＬＤ ＬＪ８０２」（日本ポリエチレン株式会社製）を用いた。
（２）接着層
・エチレン−酢酸ビニル共重合樹脂「エバフレックス３６０」（三井・デュポンポリケミカルズ株式会社製）
（３）発泡層
・ＨＩＰＳ樹脂「トーヨースチロールＨ８５０Ｎ」（東洋スチレン社製、ブタジエン含有量９．３質量％）
・ＧＰＰＳ樹脂「トーヨースチロールＧ２００Ｃ」（東洋スチレン社製）
・化学発泡剤「ＥＳ−２７５」（永和化成工業株式会社製、ポリスチレン、炭酸水素ナトリウム、タルク含量１〜１０質量％、石油系炭化水素含量１〜１０質量％）
（４）ソリッド層
・ＨＩＰＳ樹脂「トーヨースチロールＨ８５０Ｎ」（東洋スチレン社製、ブタジエン含有量９．３質量％） The resin raw materials used in the examples are as follows.
(1) Strength maintaining layer / Izod impact strength (no notch) A low-density polyethylene resin “Novatech LD LJ802” (manufactured by Nippon Polyethylene Co., Ltd.) was used as a polyolefin-based resin having 100 kJ / m 2 or more.
(2) Adhesion layer / ethylene-vinyl acetate copolymer resin “Evaflex 360” (Mitsui / DuPont Polychemicals)
(3) Foam layer / HIPS resin “Toyostyrene H850N” (manufactured by Toyo Styrene Co., Ltd., butadiene content: 9.3 mass%)
・ GPPS resin “Toyostyrene G200C” (manufactured by Toyo Styrene Co., Ltd.)
・ Chemical foaming agent “ES-275” (manufactured by Eiwa Kasei Kogyo Co., Ltd., polystyrene, sodium hydrogen carbonate, talc content 1-10% by mass, petroleum hydrocarbon content 1-10% by mass)
(4) Solid layer / HIPS resin “Toyostyrene H850N” (Toyo Styrene Co., Ltd., butadiene content: 9.3 mass%)

＜実施例１＞
４台の４０ｍｍ単軸押出機を使用し、フィードブロック法により、ソリッド層（巻き外）８０μｍ／接着層（巻き外）５μｍ／強度維持層３０μｍ／接着層（巻き内）５μｍ／発泡層３９０μｍ／ソリッド層（巻き内）２４０μｍという層構成を有する総厚み７５０μｍ（発泡層を境に強度維持層を有する側の厚み１２０μｍ）の熱可塑性多層樹脂シートを得た。 <Example 1>
Using four 40 mm single screw extruders, by a feed block method, solid layer (outside winding) 80 μm / adhesion layer (outside winding) 5 μm / strength maintaining layer 30 μm / adhesion layer (inside winding) 5 μm / foamed layer 390 μm / A thermoplastic multilayer resin sheet having a total layer thickness of 750 μm (thickness 120 μm on the side having the strength maintaining layer with the foam layer as a boundary) having a solid layer (inside winding) 240 μm layer structure was obtained.

尚、スチレン系樹脂としては、ソリッド層にはＨＩＰＳ樹脂、発泡層にはＨＩＰＳ樹脂とＧＰＰＳ樹脂を質量比５０／５０（ＨＩＰＳ／ＧＰＰＳ）で混合したものを用いた（ブタジエン成分含有量４．７質量％）。   As the styrenic resin, a HIPS resin for the solid layer and a mixture of HIPS resin and GPPS resin at a mass ratio of 50/50 (HIPS / GPPS) were used for the foam layer (butadiene component content 4.7). mass%).

また、発泡層樹脂量に対する発泡剤添加量は、０．７ＰＨＲとした。   The amount of the foaming agent added to the amount of the foam layer resin was 0.7 PHR.

この熱可塑性多層樹脂シートを下記条件で、成形、ノッチ形成、容器打ち抜き（図４）まで一連の工程で加工し、図２又は３に示す容器を得た。尚、ノッチに関しては、発泡層を境に強度維持層を有する側から形成し、ノッチの深さはノッチ形成部分の加熱温度により調整した。
使用機器：ＣＦＦ−３００（ＣＫＤ株式会社製）
上熱盤温度：１６５℃
下熱盤温度：１６５℃
ノッチ部分加熱温度：１６０℃
ノッチ深さ：３００μｍ
容器打ち抜き刃上側構造：雄刃
容器打ち抜き刃下側構造：雌刃
容器打ち抜き刃の上側下側間の間隙：２０μｍ This thermoplastic multilayer resin sheet was processed in a series of steps from molding, notch formation and container punching (FIG. 4) under the following conditions to obtain a container shown in FIG. The notch was formed from the side having the strength maintaining layer with the foam layer as a boundary, and the depth of the notch was adjusted by the heating temperature of the notch forming portion.
Equipment used: CFF-300 (manufactured by CKD Corporation)
Upper heating plate temperature: 165 ° C
Lower heating plate temperature: 165 ° C
Notch partial heating temperature: 160 ° C
Notch depth: 300 μm
Container punching blade upper structure: male blade Container punching blade lower structure: female blade Gap between upper and lower sides of container punching blade: 20 μm

得られた熱可塑性多層樹脂シート及び容器の各種評価を下記の方法で行った。結果を表１に示す。   Various evaluations of the obtained thermoplastic multilayer resin sheet and container were performed by the following methods. The results are shown in Table 1.

（１）シート比重
シートの比重を、以下の方法にて測定した。
使用機器：電子比重計ＭＤ−２００Ｓ（アルファーミラージュ株式会社製）
測定方法：試験片は、シートを３ｃｍ角にカットしたものを用いた。
測定条件：温度２５℃ (1) Sheet specific gravity The specific gravity of the sheet was measured by the following method.
Equipment used: Electronic hydrometer MD-200S (manufactured by Alpha Mirage)
Measurement method: The test piece used was a sheet cut into 3 cm square.
Measurement conditions: Temperature 25 ° C

（２）容器ノッチ折れ性
ノッチ形成部分を、図２に示す折り曲げ方向に折り曲げて、以下の基準で評価した。
◎：ノッチ３０箇所中、一回で折れない箇所が０箇所
○：ノッチ３０箇所中、一回で折れない箇所が３箇所
×：ノッチ３０箇所中、一回で折れない箇所が４〜３０箇所 (2) Container notch foldability The notch formation part was bent in the bending direction shown in FIG. 2, and evaluated according to the following criteria.
◎: 0 places that cannot be broken at one time in 30 notches ○: 3 places that cannot be folded at once in 30 places of notches ×: 4 to 30 places that cannot be folded at once in 30 places of notches

（３）容器落下強度
成形容器の落下強度を、以下の方法にて評価した。
図１に示す４連容器に水８０ｇを入れ、フィルム状の蓋材で密封した試験サンプルを２０個、作製した。これらを高さ４０ｃｍから水平に落下させ、破損した（容器から水が漏れる状態になった）サンプルの個数を記録し、以下の基準で評価した。
◎：４連容器２０個中の破損個数が０個
○：４連容器２０個中の破損個数が３個以内
×：４連容器２０個中の破損個数が４〜２０個 (3) Container drop strength The drop strength of the molded container was evaluated by the following method.
20 test samples were prepared by putting 80 g of water in the quadruple container shown in FIG. These were dropped horizontally from a height of 40 cm, and the number of broken samples (water leaked from the container) was recorded and evaluated according to the following criteria.
A: The number of breakage in 20 quadruple containers is 0. ○: The number of breakage in 20 quadruple containers is within 3. X: The number of breakages in 20 quadruple containers is 4-20.

＜実施例１〜４、比較例１〜３＞
強度維持層と接着層の有無、強度維持層の樹脂組成、発泡層樹脂量に対する発泡剤添加量、各層の厚みを表１に示すように変更した以外は実施例１と同様にして、熱可塑性多層樹脂シートを成形した。 <Examples 1-4, Comparative Examples 1-3>
Thermoplasticity in the same manner as in Example 1 except that the presence or absence of the strength maintaining layer and the adhesive layer, the resin composition of the strength maintaining layer, the added amount of the foaming agent relative to the amount of the foamed layer resin, and the thickness of each layer were changed as shown in Table 1. A multilayer resin sheet was molded.

また、得られた熱可塑性多層樹脂シートを用いて、実施例１と同様にして容器を成形した。   Moreover, the container was shape | molded like Example 1 using the obtained thermoplastic multilayer resin sheet.

評価結果を表１に示す。

Figure 0005883308
表１から明らかなように、本発明例に係る多層樹脂シートを用いて形成した容器は、容器落下強度及び容器ノッチ折れ性の何れの特性も十分良好なものであったが、比較例に係る樹脂シートを用いて形成した容器は、容器落下強度及び容器ノッチ折れ性の何れかが満足できないものであった。 The evaluation results are shown in Table 1.
Figure 0005883308
 As is clear from Table 1, the container formed using the multilayer resin sheet according to the present invention example was sufficiently good in both the container drop strength and the container notch foldability. The container formed using the resin sheet cannot satisfy either the container drop strength or the container notch foldability.

Claims (7)

発泡層を挟んで両面にソリッド層が形成され、一方の面側からノッチが形成される熱可塑性多層樹脂シートであって、ノッチ形成面を構成するソリッド層と発泡層との間に、ポリオレフィン系樹脂により形成された強度維持層が設けられ、前記発泡層を境に前記強度維持層を含むノッチ形成面側の厚みが、総厚みの２５％以下であり、前記ソリッド層がポリスチレン系樹脂により形成されてなることを特徴とする熱可塑性多層樹脂シート。 A thermoplastic multilayer resin sheet in which a solid layer is formed on both sides with a foam layer sandwiched, and a notch is formed from one side, and between the solid layer and the foam layer constituting the notch formation surface, a polyolefin-based resin sheet strength retention layer formed by a resin is provided, wherein the foam layer notching side including the strength retention layer bordering the thickness of state, and are 25% or less of the total thickness, the solid layer is a polystyrene-based resin A thermoplastic multilayer resin sheet characterized by being formed . 前記発泡層の発泡倍率が１．３〜２．０倍である請求項１に記載の熱可塑性多層樹脂シート。   The thermoplastic multilayer resin sheet according to claim 1, wherein the foaming ratio of the foamed layer is 1.3 to 2.0 times. 総厚みが６００〜１２００μｍである請求項１又は２に記載の熱可塑性多層樹脂シート。   The thermoplastic multilayer resin sheet according to claim 1 or 2, wherein the total thickness is 600 to 1200 µm. 前記発泡層がポリスチレン系樹脂により形成されてなる請求項１から３の何れか一項に記載の熱可塑性多層樹脂シート。   The thermoplastic multilayer resin sheet according to any one of claims 1 to 3, wherein the foamed layer is formed of a polystyrene-based resin. 前記強度維持層と該強度維持層に隣接する層との間に接着層を更に有する請求項１から４の何れか一項に記載の熱可塑性多層樹脂シート。 The thermoplastic multilayer resin sheet according to any one of claims 1 to 4 , further comprising an adhesive layer between the strength maintaining layer and a layer adjacent to the strength maintaining layer. 前記強度維持層が２０〜６０μｍの厚みを有する請求項１から５の何れか一項に記載の熱可塑性多層樹脂シート。 The thermoplastic multilayer resin sheet according to any one of claims 1 to 5 , wherein the strength maintaining layer has a thickness of 20 to 60 µm. 請求項１から６の何れか一項に記載の熱可塑性多層樹脂シートを熱成形してなる成形容器。 A molded container formed by thermoforming the thermoplastic multilayer resin sheet according to any one of claims 1 to 6 .
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