JP4547180B2 - Polypropylene resin laminated foam sheet and molded product thereof - Google Patents
Polypropylene resin laminated foam sheet and molded product thereof Download PDFInfo
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- JP4547180B2 JP4547180B2 JP2004105192A JP2004105192A JP4547180B2 JP 4547180 B2 JP4547180 B2 JP 4547180B2 JP 2004105192 A JP2004105192 A JP 2004105192A JP 2004105192 A JP2004105192 A JP 2004105192A JP 4547180 B2 JP4547180 B2 JP 4547180B2
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Images
Description
本発明は、ポリプロピレン系樹脂積層発泡シートおよびその成形品に関するものである。 The present invention relates to a polypropylene resin laminated foam sheet and a molded product thereof.
主にトレイ、丼、弁当箱、カップなどの食品容器の材料として、ポリプロピレン系樹脂発泡シートが広く使用されている。 Polypropylene resin foam sheets are widely used mainly as materials for food containers such as trays, bowls, lunch boxes and cups.
かかるポリプロピレン系樹脂積層発泡シートを用いて、上記食品容器などの成形品を製造するに際しては、外観を美麗にすることや内容物を映えさせることなどを目的として、その少なくとも片面に色や文様などを有するフィルムを貼り合わせることで、色や文様を有する積層発泡シートを形成した後、熱成形することが行われている。 When producing molded products such as the above-mentioned food containers using such polypropylene-based resin laminated foam sheets, colors, patterns, etc. on at least one side for the purpose of making the appearance beautiful or reflecting the contents. A laminated foamed sheet having a color and a pattern is formed by pasting together a film having, and then thermoformed.
通常色や文様などが印刷されたフィルムを発泡シートに積層する場合は、印刷の耐久性を考慮して、色や文様などが印刷された面を発泡シート側になるように配置して積層する。ところが、フィルムと発泡シートとの間に色や文様などが印刷された印刷層が介在するために、その接着強度が低くなる傾向がある。しかもフィルムと発泡シートとは、加熱による膨張や収縮の挙動が異なる。このため、かかる積層発泡シートを熱成形して得られた成形品は、例えば内容物を暖めるべく電子レンジで熱を加えた際などに両者が剥離しやすいという問題がある。 When laminating a film on which a normal color or pattern is printed on a foam sheet, in consideration of printing durability, the surface on which the color or pattern is printed is placed on the foam sheet side. . However, since a printing layer on which a color or a pattern is printed is interposed between the film and the foamed sheet, the adhesive strength tends to be lowered. Moreover, the film and the foamed sheet differ in the behavior of expansion and contraction due to heating. For this reason, a molded product obtained by thermoforming such a laminated foamed sheet has a problem that, for example, when the contents are heated in a microwave oven in order to warm the contents, both are easily peeled off.
また、発泡シートの表面には気泡による細かい凹凸が存在する。このため、色や文様などが印刷されたフィルムを発泡シートに積層した積層発泡シートから熱成形して得られた成形品は、色や文様などの美麗さが非発泡製品のそれに比べて劣る、という問題がある。 Further, fine irregularities due to bubbles exist on the surface of the foam sheet. For this reason, the molded product obtained by thermoforming from a laminated foamed sheet obtained by laminating a film on which a color or pattern is printed on a foamed sheet is inferior to that of a non-foamed product in terms of color and pattern. There is a problem.
以上のような問題を解決するために、ポリプロピレン系樹脂の発泡シートの少なくとも片面に、二軸延伸ポリプロピレン系樹脂フィルムを、当該二軸延伸ポリプロピレン系樹脂フィルム厚みの４０％以上の厚みを有する無延伸ポリプロピレン系樹脂フィルムを介して積層したポリプロピレン系樹脂積層発泡体が提案されている。（特許文献１参照） In order to solve the above-described problems, a biaxially stretched polypropylene resin film is formed on at least one surface of a polypropylene resin foam sheet, and has a thickness of 40% or more of the thickness of the biaxially stretched polypropylene resin film. There has been proposed a polypropylene resin laminate foam laminated via a polypropylene resin film. (See Patent Document 1)
また、電子レンジ調理等に使用できる耐熱性、耐油性、断熱性を有し、かつ高温時の剛性に優れるとともに、耐衝撃性および表面平滑性にも優れた成形容器が開示されている。具体的には、平均気泡径が２００〜６００μｍ、密度ρが０．１〜０．８５ｇ／ｃｍ３であるポリプロピレン系樹脂の発泡シートの少なくとも片面に、フィルム面内の互いに直交する２方向の引張破壊強さが６０〜３５０ＭＰａで、かつ両方向の引張破壊強さの比が０．３〜３．３であるポリプロピレン系樹脂のフィルムを積層してなり、積層後のフィルム側表面の表面粗さ（中心線平均粗さＲａ）が１．５μｍ以下であることを特徴とするポリプロピレン系樹脂積層発泡体から熱成形された容器が開示されている。（特許文献２）
特許文献１で開示されたポリプロピレン系樹脂積層発泡体においては、熱成形時や、電子レンジでの加熱調理時に隅部などでＯＰＰフィルムが浮き上がる問題は改善された。しかしながら、このポリプロピレン系樹脂積層発泡体の製造方法は、あらかじめ作製した発泡シート、無延伸ポリプロピレン系樹脂フィルム、および二軸延伸ポリプロピレン系樹脂フィルムを、サーマルラミネート法によって直接に積層、接着することを特徴としている。このように、押出発泡したポリプロピレン系樹脂発泡体に、無延伸ポリプロピレン系樹脂フィルムをサーマルラミネート法によって直接積層するので、二軸延伸ポリプロピレン系樹脂フィルムをサーマルラミネート法によって積層する工程と合わせて二工程を要することとなる。 In the polypropylene resin laminated foam disclosed in Patent Document 1, the problem that the OPP film is lifted at the corners during thermoforming or cooking in a microwave oven has been improved. However, this method for producing a polypropylene resin laminate foam is characterized by directly laminating and bonding a foam sheet, an unstretched polypropylene resin film, and a biaxially stretched polypropylene resin film prepared in advance by a thermal laminating method. It is said. In this way, since the unstretched polypropylene resin film is directly laminated on the extruded foamed polypropylene resin foam by the thermal laminating method, the two steps are combined with the step of laminating the biaxially stretched polypropylene resin film by the thermal laminating method. Will be required.
特許文献２も同様に、ポリプロピレン系樹脂の発泡シートの少なくとも片面に、フィルム面内の互いに直交する２方向の引張破壊強さが６０〜３５０ＭＰａで、かつ両方向の引張破壊強さの比が０．３〜３．３であるポリプロピレン系樹脂のフィルムを、共押出ではなく、サーマルラミネート法で積層するので、フィルムの積層工程が余分に必要となる。 Similarly, in Patent Document 2, the tensile fracture strength in two directions orthogonal to each other in the film plane is 60 to 350 MPa on at least one surface of the polypropylene resin foam sheet, and the ratio of the tensile fracture strength in both directions is 0. Since the polypropylene resin film of 3 to 3.3 is laminated by thermal lamination rather than coextrusion, an extra film lamination step is required.
本発明は、上記事情に鑑みてなされたものであり、すなわち本発明の目的は、色や文様などの印刷層を有する合成樹脂フィルムを積層した際でも、熱成形時やその成形品を電子レンジで加熱調理する時などに剥離しにくく耐熱性に優れる、ポリプロピレン系樹脂積層発泡シートを、より簡単な方法で製造し提供することである。 The present invention has been made in view of the above circumstances. That is, the object of the present invention is to form a microwave oven or a molded product thereof at the time of thermoforming even when a synthetic resin film having a printing layer such as a color or a pattern is laminated. It is to produce and provide a polypropylene-based resin laminated foam sheet that is difficult to peel off when heated and cooked and has excellent heat resistance by a simpler method.
また前記ポリプロピレン系樹脂積層発泡シートから熱成形された、各層間が剥離しにくく耐熱性に優れる成形品を提供することである。 It is another object of the present invention to provide a molded product that is thermoformed from the polypropylene-based resin laminated foam sheet and that is difficult to peel off between the layers and has excellent heat resistance.
請求項１に記載の本発明のポリプロピレン系樹脂積層発泡シートは、ポリプロピレン系樹脂発泡層とポリプロピレン系樹脂非発泡層とが共押出により積層されたポリプロピレン系樹脂積層発泡シートであって、該ポリプロピレン系樹脂積層発泡シート全体の密度が０．１８〜０．４５ｇ／ｃｍ3、厚みが０．５〜３．０ｍｍであり、該ポリプロピレン系樹脂積層発泡シートの全重量に対し、ポリプロピレン系樹脂発泡層が７５〜９５重量％、ポリプロピレン系樹脂非発泡層が５〜２５重量％であり、且つ該ポリプロピレン系樹脂非発泡層の表面の中心線平均粗さが０．３〜１．３μｍであって、更に、ポリプロピレン系樹脂発泡層のポリプロピレン系樹脂が、歪み硬化性を示さない（有しない）ポリプロピレン系樹脂（ａ）（以下、「ポリプロピレン系樹脂（ａ）」という）と歪み硬化性を示す（有する）ポリプロピレン系樹脂（ｂ）（以下、「ポリプロピレン系樹脂（ｂ）」という）とからなり、該歪み硬化性を示す（有する）ポリプロピレン系樹脂（ｂ）が前記ポリプロピレン系樹脂中に５〜５０重量％含まれていることを特徴とする。 The polypropylene resin laminated foam sheet of the present invention according to claim 1 is a polypropylene resin laminated foam sheet in which a polypropylene resin foam layer and a polypropylene resin non-foamed layer are laminated by coextrusion. The density of the entire resin-laminated foam sheet is 0.18 to 0.45 g / cm 3 , and the thickness is 0.5 to 3.0 mm. The polypropylene-based resin foam layer is formed with respect to the total weight of the polypropylene-based resin laminated foam sheet. 75 to 95 wt%, the polypropylene resin non-foamed layer is 5 to 25 wt%, and the center line average roughness of the surface of the polypropylene resin non-foamed layer I 0.3~1.3μm der, Furthermore, the polypropylene resin of the polypropylene resin foam layer is a polypropylene resin (a) (hereinafter referred to as “polypropylene”) that does not have (does not have strain hardening). Pyrene-based resin (a) ”) and a strain-hardening polypropylene resin (b) (hereinafter referred to as“ polypropylene-based resin (b) ”). The polypropylene resin (b) is contained in the polypropylene resin in an amount of 5 to 50% by weight .
そして、請求項２に記載の本発明のポリプロピレン系樹脂積層発泡シートは、請求項１に記載の本発明のポリプロピレン系樹脂積層発泡シートにおいて、印刷層を有する合成樹脂フィルムをその印刷層が上記ポリプロピレン系樹脂非発泡層側になるように積層してなることを特徴とする。合成樹脂フィルムとしては全体に着色したもの又は無地のものでもよい。積層方法としてはサーマルラミネート法によって積層することが好ましい。 And the polypropylene resin laminated foam sheet of this invention of Claim 2 is a polypropylene resin laminate foam sheet of this invention of Claim 1 , The synthetic resin film which has a printing layer in the said printing layer is the said polypropylene. It is characterized by being laminated so as to be on the non-foamed layer side. The synthetic resin film may be colored or plain. As a laminating method, it is preferable to laminate by a thermal laminating method.
最後に、請求項３に記載の本発明の成形品は、請求項１又は請求項２に記載のポリプロピレン系樹脂積層発泡シートを熱成形して製造されたことを特徴とする。 Finally, the molded article of the present invention described in claim 3 is manufactured by thermoforming the polypropylene resin laminated foam sheet described in claim 1 or claim 2 .
以上、詳述したように本発明のポリプロピレン系樹脂積層発泡シートによれば、このポリプロピレン系樹脂積層発泡シートに色や文様などの印刷層を有する合成樹脂フィルムを積層し熱成形しても、印刷層を有する合成樹脂フィルムが剥離することはない。また、色や文様などの印刷層を有する合成樹脂フィルムを積層したポリプロピレン系樹脂積層発泡シートから熱成形された成形品を、電子レンジで加熱調理する際などにも合成樹脂フィルムが剥離することがない。 As described above in detail, according to the polypropylene resin laminated foam sheet of the present invention, even if a synthetic resin film having a printing layer such as a color or a pattern is laminated on the polypropylene resin laminated foam sheet, the printing can be performed. The synthetic resin film having a layer does not peel off. In addition, the synthetic resin film may be peeled off when a molded product thermoformed from a polypropylene resin laminated foam sheet laminated with a synthetic resin film having a printed layer such as a color or pattern is cooked in a microwave oven. Absent.
ポリプロピレン系樹脂積層発泡シートの全重量に対し、ポリプロピレン系樹脂発泡層とポリプロピレン系樹脂非発泡層との重量を特定割合にすることで、ポリプロピレン系樹脂積層発泡シートの所望厚みを下げることなく、ポリプロピレン系樹脂非発泡層の表面の中心線平均粗さを０．３〜１．３μｍとなるように共押出することが可能となり、その結果上述した効果を得ることができる。 By setting the weight of the polypropylene resin foam layer and the polypropylene resin non-foam layer to a specific ratio with respect to the total weight of the polypropylene resin laminate foam sheet, the polypropylene resin laminate foam sheet can be reduced without reducing the desired thickness of the polypropylene resin laminate foam sheet. It becomes possible to perform co-extrusion so that the center line average roughness of the surface of the non-foamed resin layer is 0.3 to 1.3 μm, and as a result, the above-described effects can be obtained.
以下に、本発明の実施の形態を説明する。本発明のポリプロピレン系樹脂積層発泡シートの製造方法を説明する。第１押出機と第２押出機とが連結されたタンデム押出機を使用し、第１押出機のホッパーから、ポリプロピレン系樹脂（ａ）およびポリプロピレン系樹脂（ｂ）を供給し、加熱溶融した後、物理発泡剤を圧入して溶融混合する。その後第２押出機に移送して発泡適正温度まで冷却して発泡性溶融樹脂とし、第２押出機先端に接続された合流環状ダイスへ移送する。 Hereinafter, embodiments of the present invention will be described. The manufacturing method of the polypropylene resin laminated foam sheet of this invention is demonstrated. After supplying the polypropylene resin (a) and the polypropylene resin (b) from the hopper of the first extruder and heating and melting them using a tandem extruder in which the first extruder and the second extruder are connected. Then, a physical foaming agent is injected and melt mixed. Thereafter, it is transferred to a second extruder, cooled to an appropriate foaming temperature, made into a foamable molten resin, and transferred to a converging annular die connected to the tip of the second extruder.
一方、シングル押出機を使用して、シングル押出機のホッパーからポリプロピレン系樹脂を供給し、加熱溶融した後、前記合流環状ダイスへ移送し、前記発泡性溶融樹脂と合流させて積層した後、円筒状押出口を有するサーキュラー金型より押出発泡させて、ポリプロピレン系樹脂発泡層とポリプロピレン系樹脂非発泡層とが積層されたポリプロピレン系樹脂積層発泡シートを得る。 On the other hand, using a single extruder, a polypropylene resin is supplied from a hopper of a single extruder, heated and melted, then transferred to the merging annular die, merged with the foamable molten resin, laminated, and then cylindrical A polypropylene resin laminated foam sheet in which a polypropylene resin foam layer and a polypropylene resin non-foamed layer are laminated is obtained by extrusion foaming from a circular mold having a cylindrical extrusion port.
ここで、シングル押出機に供給するポリプロピレン系樹脂としては、ポリプロピレン系樹脂（ａ）またはポリプロピレン系樹脂（ｂ）でも良いし、それらの混合樹脂でも良い。但し、メルトマスフローレイトが３〜２０ｇ／１０分のものが好ましい。メルトマスフローレイトが３ｇ／１０分未満だと、樹脂が伸びず金型の形状に沿って樹脂が広がらず、ポリプロピレン系樹脂非発泡層の表面の中心線平均粗さが０．３〜１．３μｍとならない。また、メルトマスフローレイトが２０ｇ／１０分を超えると、樹脂の張力が低すぎて、ポリプロピレン系樹脂積層発泡シートが押出成形できない。 Here, the polypropylene resin supplied to the single extruder may be a polypropylene resin (a), a polypropylene resin (b), or a mixed resin thereof. However, those having a melt mass flow rate of 3 to 20 g / 10 min are preferred. When the melt mass flow rate is less than 3 g / 10 minutes, the resin does not stretch and does not spread along the shape of the mold, and the center line average roughness of the surface of the polypropylene resin non-foamed layer is 0.3 to 1.3 μm. Not. On the other hand, if the melt mass flow rate exceeds 20 g / 10 min, the tension of the resin is too low and the polypropylene-based resin laminated foam sheet cannot be extruded.
メルトマスフローレイトの測定は、ＪＩＳ Ｋ ７２１０：１９９９「プラスチック熱可塑性プラスチックのメルトマスフローレイト（ＭＦＲ）及びメルトボリュームフローレイト（ＭＶＲ）の試験方法」Ｂ法記載の方法により測定する。実際の測定方法としては、測定装置（セミオートメルトインデクサー（（株）東洋精機製作所製）のシリンダーに試料を３〜８ｇ充填し、充填棒を用いて材料を圧縮する。試験温度は２３０℃（ＰＰ）で、試験荷重は、規定荷重（２１．１８Ｎ（ＰＰ、ＰＥ）による。予熱時間は４分、試験数は３個とする。 The melt mass flow rate is measured by the method described in JIS K 7210: 1999 “Testing Method for Melt Mass Flow Rate (MFR) and Melt Volume Flow Rate (MVR) of Plastic Thermoplastic” B method. As an actual measuring method, 3 to 8 g of a sample is filled in a cylinder of a measuring apparatus (semi-auto melt indexer (manufactured by Toyo Seiki Seisakusho Co., Ltd.)), and the material is compressed using a filling rod. In PP, the test load depends on the specified load (21.18N (PP, PE). The preheating time is 4 minutes and the number of tests is 3.
本発明における「歪み硬化性」とは、ポリプロピレン系樹脂の伸長粘度測定において、伸長粘度が歪み速度の増加に伴って急激に上昇する特性を意味する。具体的には、東洋精機製作所（株）製のメルテンレオメータを使用し、ポリプロピレン系樹脂をロッド状に成形したサンプルを準備し、成形時の残留歪みの影響をなくすために１８０℃に温調された測定用バス中に５分ほど保持した後、測定用バス中（シリコーンオイル中）でサンプルの両端をクランプロールで挟み、該サンプルを一定の歪み速度（０．５ｓｅｃ-1）で伸張させたときに、伸張中の試料にかかる張力および外形を測定する。得られた張力および外形から算出された伸張粘度を時間に対してプロットすると、ポリプロピレン系樹脂（ｂ）では、図１に実線で示すように、伸張粘度が時間の経過と共に大きくなり、ある点でそれまでの上昇度合いに比べて急激に増大する傾向を示す。一方、ポリプロピレン系樹脂（ａ）では、図１に点線で示すように、時間と共に伸張粘度は増加するが、上記のように伸張粘度が急激に増加する挙動を示さず、ある時点で粘度は減少するか、あるいはサンプルが破断してしまう。 The “strain curable” in the present invention means a characteristic that the extensional viscosity rapidly increases as the strain rate increases in the measurement of the extensional viscosity of the polypropylene resin. Specifically, a melten rheometer manufactured by Toyo Seiki Seisakusho Co., Ltd. was used to prepare a sample in which a polypropylene resin was molded into a rod shape, and the temperature was adjusted to 180 ° C to eliminate the effect of residual strain during molding. After holding the sample in the measurement bath for about 5 minutes, sandwich both ends of the sample in the measurement bath (silicone oil) with clamp rolls and stretch the sample at a constant strain rate (0.5 sec-1). Measure the tension and external shape applied to the stretching sample. When the extensional viscosity calculated from the obtained tension and outer shape is plotted against time, in the polypropylene resin (b), as shown by the solid line in FIG. 1, the extensional viscosity increases with the passage of time. It shows a tendency to increase abruptly compared with the degree of increase up to that point. On the other hand, in the polypropylene resin (a), as shown by the dotted line in FIG. 1, the extensional viscosity increases with time, but the behavior of the extensional viscosity increasing rapidly as described above is not shown, and the viscosity decreases at a certain point. Or the sample breaks.
ポリプロピレン系樹脂（ａ）としては、市販の一般的な直鎖状ポリプロピレン系樹脂、例えばサンアロマー（株）製のＰＭ６００Ａ、ＰＭ５００Ａなどが挙げられる。また、ポリプロピレン系樹脂（ｂ）の例としては、電子線照射または化学的架橋によって分岐構造を分子鎖に導入したポリプロピレン系樹脂、あるいは超高分子量成分を混合することによって分子鎖同士の絡み合いを大きくしたポリプロピレン系樹脂が挙げられ、具体的には例えば、Ｂａｓｅｌｌ社製のＰＦ−８１４およびＳＤ−６３２など、ならびにＢＯＲＥＡＬＩＳ社製のＷＢ１３０ＨＭＳなどが挙げられる。 Examples of the polypropylene resin (a) include commercially available general linear polypropylene resins such as PM600A and PM500A manufactured by Sun Allomer Co., Ltd. Examples of the polypropylene resin (b) include a polypropylene resin in which a branched structure is introduced into a molecular chain by electron beam irradiation or chemical crosslinking, or a mixture of ultrahigh molecular weight components to greatly increase the entanglement between molecular chains. Specific examples thereof include PF-814 and SD-632 manufactured by Basell, and WB130HMS manufactured by BOREALIS.
ポリプロピレン系樹脂（ａ）およびポリプロピレン系樹脂（ｂ）は、それぞれ１種類ずつ混合される場合に限らず、ポリプロピレン系樹脂（ｂ）を少なくとも１種類含めば、ポリプロピレン系樹脂（ａ）は２種類以上であってもよい。ポリプロピレン系樹脂（ａ）とポリプロピレン系樹脂（ｂ）との配合割合は、通常、ポリプロピレン系樹脂（ａ）５０〜９５重量％に対して、ポリプロピレン系樹脂（ｂ）が５〜５０重量％である。ポリプロピレン系樹脂（ｂ）の配合割合が５重量％を下回ると、押出発泡性が低下し、独立気泡率の高い高倍の発泡体が得られず、耐熱性と機械的強度に優れた発泡体とならない。また、ポリプロピレン系樹脂（ｂ）の配合割合が５０重量％を超えても、加えた以上の効果は得られない。 The polypropylene resin (a) and the polypropylene resin (b) are not limited to being mixed one by one, but if at least one polypropylene resin (b) is included, two or more polypropylene resins (a) are included. It may be. The blending ratio of the polypropylene resin (a) and the polypropylene resin (b) is usually 5 to 50% by weight of the polypropylene resin (b) with respect to 50 to 95% by weight of the polypropylene resin (a). . When the blending ratio of the polypropylene resin (b) is less than 5% by weight, the extrusion foamability is lowered, and a high-fold foam having a high closed cell ratio cannot be obtained, and a foam excellent in heat resistance and mechanical strength is obtained. Don't be. Moreover, even if the blending ratio of the polypropylene resin (b) exceeds 50% by weight, the effect more than that added cannot be obtained.
本発明の製造方法で用いられる発泡剤としては、種々の揮発性発泡剤や分解型発泡剤、あるいは二酸化炭素、窒素ガス、水等が挙げられる。このうち揮発性発泡剤としては、例えばプロパン、ブタン、ペンタン等の炭化水素や、テトラフルオロエタン、クロロジフルオロエタン、ジフルオロエタン等のハロゲン化炭化水素などの１種または２種以上が挙げられ、特にブタンが好適に使用される。ブタンとしてはノルマルブタン、もしくはイソブタンをそれぞれ単独で使用してもよいし、ノルマルブタンとイソブタンとを任意の割合で併用してもよい。また分解型発泡剤としては、例えばアゾジカルボンアミド、ジニトロソペンタメチレンテトラミンなどの有機系発泡剤、クエン酸等の有機酸もしくはその塩と、重炭酸ナトリウム等の重炭酸塩との組み合わせなどの無機系発泡剤が挙げられる。これらの発泡剤はいずれかを１種単独で使用してもよいし、２種以上を併用してもよい。 Examples of the foaming agent used in the production method of the present invention include various volatile foaming agents, decomposable foaming agents, carbon dioxide, nitrogen gas, and water. Among these, examples of the volatile blowing agent include one or more hydrocarbons such as propane, butane and pentane, and halogenated hydrocarbons such as tetrafluoroethane, chlorodifluoroethane and difluoroethane. Preferably used. As butane, normal butane or isobutane may be used alone, or normal butane and isobutane may be used in any proportion. Examples of the decomposable foaming agent include inorganic foaming agents such as an organic foaming agent such as azodicarbonamide and dinitrosopentamethylenetetramine, a combination of an organic acid such as citric acid or a salt thereof, and a bicarbonate such as sodium bicarbonate. Type foaming agents. One of these foaming agents may be used alone, or two or more thereof may be used in combination.
またポリプロピレン系樹脂にはあらかじめ、または押出機で溶融混練する際に、例えばタルクや、あるいはクエン酸と重炭酸ナトリウム等の、発泡の際に気泡の大きさを調整するための気泡調整剤や、顔料、安定剤、充てん剤、帯電防止剤等の種々の添加剤を、本発明の効果を損なわない範囲で適宜添加してもよい。このうち充てん剤は、成形品の強度、高温での剛性、耐久性および耐熱性を向上するために添加されるもので、かかる充てん剤としては、例えばタルク、炭酸カルシウム、シリカ、アルミナ、酸化チタン、クレー等の無機充てん剤が挙げられる。無機充てん剤の添加量は、ポリプロピレン系樹脂１００重量部に対して０．０５〜１０重量部であるのが好ましい。 In addition, when melt-kneaded with a polypropylene-based resin in advance or with an extruder, for example, talc, or citric acid and sodium bicarbonate, such as a bubble adjusting agent for adjusting the size of bubbles when foaming, Various additives such as pigments, stabilizers, fillers, antistatic agents and the like may be appropriately added within a range not impairing the effects of the present invention. Among them, the filler is added to improve the strength of the molded product, rigidity at high temperature, durability and heat resistance. Examples of the filler include talc, calcium carbonate, silica, alumina, and titanium oxide. And inorganic fillers such as clay. The addition amount of the inorganic filler is preferably 0.05 to 10 parts by weight with respect to 100 parts by weight of the polypropylene resin.
かくして形成されるポリプロピレン系樹脂積層発泡シートは、その全体の密度が０．１８〜０．４５ｇ／ｃｍ３であるものが好ましい。ポリプロピレン系樹脂積層発泡シート全体の密度が０．１８ｇ／ｃｍ３未満では、成形品に成形した際の強度や高温での剛性が低下するおそれがあり、逆に０．４５ｇ／ｃｍ３を超えた場合には、成形品の断熱性が低下するおそれがある。なおポリプロピレン系樹脂積層発泡シート全体の密度は、成形品の強度や剛性と、断熱性とのバランスを考慮すると、上記の範囲内でも特に０．２０〜０．３０ｇ／ｃｍ３であるのが好ましい。 The polypropylene-based resin laminated foam sheet thus formed preferably has a total density of 0.18 to 0.45 g / cm 3 . If the density of the entire polypropylene-based resin laminated foam sheet is less than 0.18 g / cm 3 , the strength at the time of molding into a molded product and the rigidity at high temperature may be lowered, and conversely, it exceeds 0.45 g / cm 3 . In such a case, the heat insulating property of the molded product may be reduced. The density of the entire polypropylene-based resin laminated foam sheet is preferably 0.20 to 0.30 g / cm 3 even in the above range, considering the balance between the strength and rigidity of the molded product and the heat insulation. .
ポリプロピレン系樹脂積層発泡シート全体の密度は、ポリプロピレン系樹脂積層発泡シート全体の重量と体積とを測定して、重量（ｇ）÷体積（ｃｍ３）により求めた。
また、ポリプロピレン系樹脂積層発泡シートの厚みは、目的とする成形品の仕様などにもよるが、熱成形性を勘案すると０．５〜３．０ｍｍであるのが好ましく、０．７〜２．５ｍｍであるのがさらに好ましい。
The density of the entire polypropylene-based resin laminated foam sheet was obtained by measuring the weight and volume of the entire polypropylene-based resin laminated foam sheet and calculating the weight (g) / volume (cm 3 ).
Moreover, although the thickness of a polypropylene resin laminated foam sheet is based also on the specification of the target molded article, etc., when considering thermoformability, it is preferable that it is 0.5-3.0 mm, 0.7-2. More preferably, it is 5 mm.
そして、ポリプロピレン系樹脂積層発泡シートの全重量に対し、ポリプロピレン系樹脂発泡層が７５〜９５重量％、ポリプロピレン系樹脂非発泡層が５〜２５重量％であることが好ましい。ポリプロピレン系樹脂発泡層が７５重量％未満でポリプロピレン系樹脂非発泡層が２５重量％を超えると、ポリプロピレン系樹脂積層発泡シート全体の倍率が小さくなり、所望の軽量性や断熱性が得られず好ましくない。一方、ポリプロピレン系樹脂発泡層が９５重量％を超えてポリプロピレン系樹脂非発泡層が５重量％未満では、ポリプロピレン系樹脂非発泡層の表面の中心線平均粗さが０．３〜１．３μｍの範囲におさまらない。そのため、印刷層を有する合成樹脂フィルムをその印刷層が上記ポリプロピレン系樹脂非発泡層側になるように積層したりした場合に、それらの積層面の積層強度が低下し、ポリプロピレン系樹脂積層発泡シートの熱成形時やその成形品を電子レンジで加熱調理する際などに剥離しやすくなる。ポリプロピレン系樹脂積層発泡シートの全重量に対し、ポリプロピレン系樹脂発泡層が８０〜９０重量％、ポリプロピレン系樹脂非発泡層が１０〜２０重量％であることが更に好ましい。 And it is preferable that a polypropylene resin foam layer is 75 to 95 weight% and a polypropylene resin non-foamed layer is 5 to 25 weight% with respect to the total weight of a polypropylene resin laminated foam sheet. When the polypropylene resin foam layer is less than 75% by weight and the polypropylene resin non-foam layer exceeds 25% by weight, the overall magnification of the polypropylene resin laminate foam sheet is decreased, and desired lightness and heat insulation cannot be obtained. Absent. On the other hand, when the polypropylene resin foam layer exceeds 95% by weight and the polypropylene resin non-foam layer is less than 5% by weight, the center line average roughness of the surface of the polypropylene resin non-foam layer is 0.3 to 1.3 μm. Does not fit in range. Therefore, when a synthetic resin film having a printed layer is laminated so that the printed layer is on the polypropylene resin non-foamed layer side, the lamination strength of those laminated surfaces is reduced, and the polypropylene resin laminated foam sheet It becomes easy to peel off at the time of thermoforming or when the molded product is cooked in a microwave oven. More preferably, the polypropylene resin foamed layer is 80 to 90% by weight and the polypropylene resin non-foamed layer is 10 to 20% by weight based on the total weight of the polypropylene resin laminated foamed sheet.
また、ポリプロピレン系樹脂非発泡層の表面の中心線平均粗さを０．３〜１．３μｍの範囲にするために、ポリプロピレン系樹脂非発泡層の重量を増やすと、所望の厚みが得られなくなるため、ポリプロピレン系樹脂発泡層の倍率を上げる必要がある。しかし、ポリプロピレン系樹脂発泡層の倍率を上げると、発泡層の連続気泡率が増えて、ポリプロピレン系樹脂積層発泡シートの強度が低下してしまう。このため、ポリプロピレン系樹脂積層発泡シートの全重量に対し、ポリプロピレン系樹脂発泡層が７５〜９５重量％、ポリプロピレン系樹脂非発泡層が５〜２５重量％であることが好ましい。 Moreover, when the weight of the polypropylene resin non-foamed layer is increased in order to make the center line average roughness of the surface of the polypropylene resin non-foamed layer in the range of 0.3 to 1.3 μm, a desired thickness cannot be obtained. Therefore, it is necessary to increase the magnification of the polypropylene resin foam layer. However, when the magnification of the polypropylene resin foam layer is increased, the open cell ratio of the foam layer increases, and the strength of the polypropylene resin laminate foam sheet decreases. For this reason, it is preferable that a polypropylene resin foam layer is 75 to 95 weight% and a polypropylene resin non-foamed layer is 5 to 25 weight% with respect to the total weight of a polypropylene resin laminated foam sheet.
これらポリプロピレン系樹脂発泡層の重量と、ポリプロピレン系樹脂非発泡層の重量の調整は、それぞれの押出量を制御することで行うことができる。 Adjustment of the weight of these polypropylene resin foamed layers and the weight of a polypropylene resin non-foamed layer can be performed by controlling each extrusion amount.
各重量％の測定方法は以下の様に行った。
ポリプロピレン系樹脂積層発泡シートを、ＴＤ方向とＶＤ方向に平行な向きに切断し、その切断面を電顕にて４０倍で撮影する。また、前記発泡シートをＭＤ方向とＶＤ方向に平行な向きに切断し、その切断面を電顕にて４０倍で撮影する。それぞれの電顕写真上にてフィルムの厚みを測定し、（ポリプロピレン系樹脂積層発泡シートの非発泡層の表面から発泡層に存する一番上の気泡の界面までの距離を測定する。測定は写真上で実際寸法で１ｍｍの間隔をおいて３箇所をはかり、その平均値とする。）それらの平均値を厚みとする。その厚みの単位をｍに換算し、ポリプロピレン系樹脂の比重（０．９）をかけて、非発泡層の坪量（ｇ／ｍ２）を算出する。そして、ポリプロピレン系樹脂積層発泡シート全体の坪量を測定した上で、前記ポリプロピレン系樹脂積層発泡シート全体の坪量から前記非発泡層の坪量を引いた値を、発泡層の坪量とする。そしてそれぞれの坪量から、各層の重量％を算出する。
The measurement method of each weight% was performed as follows.
The polypropylene-based resin laminated foam sheet is cut in a direction parallel to the TD direction and the VD direction, and the cut surface is photographed 40 times with an electron microscope. Further, the foam sheet is cut in a direction parallel to the MD direction and the VD direction, and the cut surface is photographed 40 times with an electron microscope. The thickness of the film is measured on each electron micrograph, and the distance from the surface of the non-foamed layer of the polypropylene resin laminated foam sheet to the interface of the uppermost bubble existing in the foamed layer is measured. 3 points are measured at an interval of 1 mm in actual dimensions above, and the average value is taken.) The average value is taken as the thickness. The unit of the thickness is converted into m, and the basis weight (g / m 2 ) of the non-foamed layer is calculated by multiplying the specific gravity (0.9) of the polypropylene resin. And after measuring the basic weight of the whole polypropylene resin laminated foam sheet, the value which subtracted the basic weight of the said non-foamed layer from the basic weight of the said polypropylene resin laminated foam sheet is made into the basic weight of a foam layer. . And the weight% of each layer is calculated from each basis weight.
ポリプロピレン系樹脂非発泡層の表面の中心線平均粗さは０．３〜１．３μｍであることが好ましい。中心線平均粗さが０μｍに近い程好ましいが、製造上０．３μｍまでが限界である。また、中心線平均粗さが１．３μｍを超えると、印刷層を有する合成樹脂フィルムをその印刷層が上記ポリプロピレン系樹脂非発泡層側になるように積層した場合に、剥離強度が弱くなってしまう。 The center line average roughness of the surface of the polypropylene resin non-foamed layer is preferably 0.3 to 1.3 μm. The center line average roughness is preferably closer to 0 μm, but is limited to 0.3 μm in production. Moreover, when the center line average roughness exceeds 1.3 μm, when the synthetic resin film having the printing layer is laminated so that the printing layer is on the polypropylene resin non-foamed layer side, the peel strength becomes weak. End up.
表面の中心線平均粗さは、下記の様にして測定した。中心線平均粗さは、(株)東京精密製の表面粗さ計ハンディーサーフＥ−３５Ａを使用して求めた。このハンディーサーフＥ−３５Ａは、サンプル表面の断面曲線を測定し、その結果から、ＪＩＳ Ｂ０６０１−１９９４「表面粗さ−定義及び表示」に規定された方法に基づいて自動的に演算をして、中心線平均粗さを出力する機能を有するものである。 The centerline average roughness of the surface was measured as follows. The centerline average roughness was determined using a surface roughness meter Handy Surf E-35A manufactured by Tokyo Seimitsu Co., Ltd. This Handy Surf E-35A measures the cross-sectional curve of the sample surface, and from the result, automatically calculates based on the method specified in JIS B0601-1994 "Surface Roughness-Definition and Display", It has a function of outputting the center line average roughness.
具体的には、ポリプロピレン系樹脂積層発泡シートにおけるポリプロピレン系樹脂非発泡層側表面の、ＭＤ方向とＴＤ方向の２方向について、それぞれハンディーサーフＥ−３５Ａを用いて測定を行って、２方向の中心線平均粗さを求めた。そしてこの２方向の中心線平均粗さの平均値を計算して、サンプルの中心線平均粗さとした。なお測定条件はいずれも、カットオフ値を０．８ｍｍ、測定長さを、カットオフ値の５倍の４ｍｍとした。 Specifically, the two directions of the MD direction and the TD direction on the surface of the polypropylene resin non-foamed layer side in the polypropylene resin laminated foam sheet are measured using Handy Surf E-35A, respectively, and the center of the two directions is measured. The line average roughness was determined. And the average value of the center line average roughness of these 2 directions was calculated, and it was set as the center line average roughness of the sample. In all the measurement conditions, the cut-off value was 0.8 mm, and the measurement length was 4 mm, which is five times the cut-off value.
以下に本発明の実施例を詳細に説明するが、これらの実施例は本発明の範囲を限定するものではない。 Examples of the present invention will be described in detail below, but these examples do not limit the scope of the present invention.
歪み硬化性を有しないポリプロピレン系樹脂として、サンアロマー社製のＰＭ６００Ａ（７５重量％）と、歪み硬化性を有するポリプロピレン系樹脂として、Ｂａｓｅｌｌ社製のＳＤ６３２（２５重量％）とを混合し、この混合樹脂１００重量部に対して、気泡調整剤として、クラリアント社製のＨＫ−７０を０．２重量部添加してドライブレンドした。そしてこの混合原料を、口径９０ｍｍ−１１５ｍｍの第１押出機および第２押出機からなるタンデム押出機における第１押出機のホッパーに供給し、加熱溶融した後、発泡剤としてブタン（イソブタン／ノルマルブタン＝３５／６５）１．０重量部を圧入し、溶融混合させた。その後、第２押出機に移送して発泡適正温度まで冷却して発泡性溶融樹脂とした。一方、歪み硬化性を有しないポリプロピレン系樹脂として、三井住友ポリオレフィン社製のＪ１０４ＷＡを口径９０ｍｍのシングル押出機のホッパーに投入し、加熱溶融した。そして、口径９０ｍｍ−１１５ｍｍのタンデム押出機の樹脂が８０重量％、一方口径９０ｍｍシングル押出機の樹脂が２０重量％となるように、各押出量を調整し、各押出機内の発泡性溶融樹脂と溶融樹脂とを合流環状ダイスで合流させて積層した後、口径１９０ｍｍの円筒状押出口を有するサーキュラー金型より吐出量２００ｋｇ／時間で押出発泡させた。得られた円筒状発泡体を、内部が約２５℃の水で冷却されている口径６７０ｍｍのマンドレル上を沿わせ、またその外面をその径よりも大きい空冷装置（エアーリング）によりエアーを吹き付けることにより冷却成形し、マンドレル下流側に固定された円周上の２点でカッターにより切開し表１に示す物性の積層発泡シートを得た。 PM600A (75% by weight) manufactured by Sun Allomer as a polypropylene resin not having strain hardening and SD632 (25% by weight) manufactured by Basell as a polypropylene resin having strain hardening are mixed. To 100 parts by weight of the resin, 0.2 parts by weight of HK-70 manufactured by Clariant Co., Ltd. was added as a foam regulator and dry blended. And this mixed raw material is supplied to the hopper of the 1st extruder in the tandem extruder which consists of a 1st extruder and a 2nd extruder with a diameter of 90 mm-115 mm, and after heat-melting, it is butane (isobutane / normal butane) as a foaming agent. = 35/65) 1.0 part by weight was injected and melt-mixed. Then, it transferred to the 2nd extruder and cooled to foaming appropriate temperature, and it was set as the foamable molten resin. On the other hand, J104WA manufactured by Sumitomo Mitsui Polyolefin Co., Ltd. was introduced into a hopper of a single extruder having a diameter of 90 mm as a polypropylene resin having no strain-hardening property, and was melted by heating. And each extrusion amount was adjusted so that the resin of a tandem extruder having a diameter of 90 mm to 115 mm would be 80% by weight, and the resin of a single extruder having a diameter of 90 mm would be 20% by weight, and the foamable molten resin in each extruder The molten resin was joined with a joining annular die and laminated, and then extruded and foamed at a discharge rate of 200 kg / hour from a circular mold having a cylindrical extrusion port with a diameter of 190 mm. The obtained cylindrical foam is placed on a mandrel having a diameter of 670 mm, the inside of which is cooled with water at about 25 ° C., and the outer surface is blown with an air cooling device (air ring) larger than the diameter. The laminate foam sheet having physical properties shown in Table 1 was obtained by cutting with a cutter at two points on the circumference fixed on the downstream side of the mandrel.
実施例２〜４ならびに比較例１〜３については、表１に示す原料と各原料の配合割合を変えて、後は実施例１と同様に行った。以上得られた積層発泡シートの物性を表１に記載した。表１中の％は重量％、部は重量部を意味する。 About Examples 2-4 and Comparative Examples 1-3, the compounding ratio of the raw material shown in Table 1 and each raw material was changed, and it carried out similarly to Example 1 after that. The physical properties of the laminated foam sheet obtained above are shown in Table 1. In Table 1, “%” means “% by weight” and “part” means “part by weight”.
本発明のポリプロピレン系樹脂積層発泡シートおよびその成形品は、耐熱性を要求される食品用容器に好適に利用できる。 The polypropylene resin laminated foam sheet of the present invention and its molded product can be suitably used for food containers that require heat resistance.
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| JPH11277696A (en) * | 1998-02-02 | 1999-10-12 | Jsp Corp | Propylene resin foamed laminated flat sheet and its production |
| JP2001113653A (en) * | 1999-08-12 | 2001-04-24 | Sumitomo Chem Co Ltd | Multilayered polyolefin foamed sheet |
| JP2001315277A (en) * | 2000-03-02 | 2001-11-13 | Sekisui Plastics Co Ltd | Polypropylene resin-laminated foam and molded container using the foam |
| JP2002166510A (en) * | 2000-11-30 | 2002-06-11 | Sumitomo Chem Co Ltd | Polyolefinic resin foamed sheet |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH11277696A (en) * | 1998-02-02 | 1999-10-12 | Jsp Corp | Propylene resin foamed laminated flat sheet and its production |
| JP2001113653A (en) * | 1999-08-12 | 2001-04-24 | Sumitomo Chem Co Ltd | Multilayered polyolefin foamed sheet |
| JP2001315277A (en) * | 2000-03-02 | 2001-11-13 | Sekisui Plastics Co Ltd | Polypropylene resin-laminated foam and molded container using the foam |
| JP2002166510A (en) * | 2000-11-30 | 2002-06-11 | Sumitomo Chem Co Ltd | Polyolefinic resin foamed sheet |
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| US10059037B2 (en) | 2014-09-23 | 2018-08-28 | Dart Container Corporation | Insulated container and methods of making and assembling |
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