JP2006051603A - Polystyrenic resin laminated foamed sheet - Google Patents
Polystyrenic resin laminated foamed sheet Download PDFInfo
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- JP2006051603A JP2006051603A JP2004229261A JP2004229261A JP2006051603A JP 2006051603 A JP2006051603 A JP 2006051603A JP 2004229261 A JP2004229261 A JP 2004229261A JP 2004229261 A JP2004229261 A JP 2004229261A JP 2006051603 A JP2006051603 A JP 2006051603A
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- 238000005187 foaming Methods 0.000 claims abstract description 23
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- JQXYBDVZAUEPDL-UHFFFAOYSA-N 2-methylidene-5-phenylpent-4-enoic acid Chemical compound OC(=O)C(=C)CC=CC1=CC=CC=C1 JQXYBDVZAUEPDL-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- FEIQOMCWGDNMHM-UHFFFAOYSA-N 5-phenylpenta-2,4-dienoic acid Chemical compound OC(=O)C=CC=CC1=CC=CC=C1 FEIQOMCWGDNMHM-UHFFFAOYSA-N 0.000 description 1
- 239000004156 Azodicarbonamide Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
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- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
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- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
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- ADFPJHOAARPYLP-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;styrene Chemical compound COC(=O)C(C)=C.C=CC1=CC=CC=C1 ADFPJHOAARPYLP-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
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Abstract
Description
本発明は、ポリスチレン系樹脂積層発泡シートに関し、特に広い範囲の加熱成形条件にて印刷性に優れる容器を成形可能なポリスチレン系樹脂積層発泡シートに関する。 The present invention relates to a polystyrene-based resin laminated foam sheet, and more particularly, to a polystyrene-based resin laminated foam sheet capable of forming a container having excellent printability under a wide range of thermoforming conditions.
ポリスチレン系樹脂積層発泡シートは、加熱成形による成形体を得るための成形用シートとして従来から広く利用されてきた。このポリスチレン系樹脂積層発泡シート（以下、単に積層発泡シートともいう。）は、ポリスチレン系樹脂発泡シートに耐衝撃性を有するポリスチレン系樹脂層が積層されたシートである。該積層発泡シートは、押出機を用いてポリスチレン系樹脂と気泡調整剤等の各種の添加剤と発泡剤とを溶融混練することによって発泡性溶融混合樹脂とし、該発泡性溶融混合樹脂を、高圧のダイ内から大気圧下に放出することによってポリスチレン系樹脂発泡シートを形成した後、耐衝撃性ポリスチレン系樹脂層を積層したり、発泡性溶融混合樹脂と耐衝撃性ポリスチレン系樹脂溶融物を共押出すること等によって製造される。 BACKGROUND ART A polystyrene-based resin laminated foam sheet has been widely used as a molding sheet for obtaining a molded body by heat molding. This polystyrene-based resin laminated foamed sheet (hereinafter also simply referred to as a laminated foamed sheet) is a sheet in which a polystyrene-based resin layer having impact resistance is laminated on a polystyrene-based resin foamed sheet. The laminated foam sheet is made into a foamable melt-mixed resin by melt-kneading a polystyrene resin, various additives such as a bubble regulator and a foaming agent using an extruder, After forming a polystyrene resin foam sheet by releasing from the inside of the die under atmospheric pressure, an impact-resistant polystyrene resin layer is laminated, or a foamable molten mixed resin and an impact-resistant polystyrene resin melt are used together. Manufactured by extruding.
このようにして得られた積層発泡シートを加熱成形してなる発泡シート成形体（以下、単に成形体ともいう。）は、断熱性に優れ、しかも軽量で安価なことから広く使用されている。
しかし、従来の成形体は、成形直後の印刷性が劣るという問題を有していた。即ち、積層発泡シートを加熱成形することによって得られた成形体は、商品価値の向上のため、その外側側面に図柄や文字などの曲面印刷が施される。ところが、従来の成形体は、加熱成形後長時間経過後であれば美麗な印刷を施すことができるが、生産性を向上させるために加熱成形直後に印刷すると、印刷かすれ等の印刷不良が発生しやすく、商品価値がなくなるという欠点を有していた。
A foamed sheet molded body (hereinafter, simply referred to as a molded body) obtained by heat-molding the laminated foamed sheet thus obtained is widely used because of its excellent heat insulation, light weight, and low cost.
However, the conventional molded body has a problem that printability immediately after molding is poor. That is, the molded body obtained by heat-molding the laminated foam sheet is subjected to curved surface printing such as symbols and characters on the outer side surface in order to improve the commercial value. However, conventional molded products can be printed beautifully if a long time has passed after thermoforming. However, if printing is performed immediately after thermoforming in order to improve productivity, printing defects such as blurring occur. It was easy to do and had the disadvantage that the commercial value was lost.
積層発泡シートを加熱成形した直後の成形体において印刷不良が発生しやすいのは、積層発泡シートを構成するポリスチレン系樹脂発泡層中の気泡中の圧力が減圧状態にあり圧縮強度が低いことから、強い印圧で印刷することができないことによるものである。従って、低い印圧であっても美麗な印刷が可能な成形体を製造することができる積層発泡シートの開発が望まれてきた。具体的には、成形容器の表面粗さが小さければ低い印圧でも、印刷ぬけと呼ばれる印刷時にインキの一部分抜け落ちる箇所が発生する等の印刷不良が発生しないと考えられることから、容器の表面粗さを小さくすることが試みられてきた。尚、加熱成形直後の成形体を構成する気泡中の圧力が減圧状態になるのは、加熱成形時の加熱によりシートが発泡し、延伸されることによって体積が増大し気泡内の気圧が低くなることによるものである。 The reason why print defects are likely to occur in a molded article immediately after thermoforming the laminated foam sheet is that the pressure in the bubbles in the polystyrene resin foam layer constituting the laminated foam sheet is in a reduced pressure state and the compression strength is low. This is because printing cannot be performed with a strong printing pressure. Therefore, it has been desired to develop a laminated foamed sheet that can produce a molded body capable of beautiful printing even at a low printing pressure. Specifically, if the surface roughness of the molded container is small, even if the printing pressure is low, it is considered that printing defects such as the occurrence of a part of ink falling off during printing, which is called printing printing, will not occur. Attempts have been made to reduce the size. In addition, the pressure in the bubbles constituting the molded body immediately after the heat forming is reduced. The reason is that the sheet is foamed by the heating at the time of heat forming, and the volume is increased by stretching and the pressure in the bubbles is lowered. It is because.
一方、成形体の表面粗さを小さくする技術としては、例えば特開平９−２７２１６５号公報（特許文献１）に開示されたものがある。特許文献１には、積層発泡シートの密度が最低になるように２次発泡させた後の圧縮変形量が０．５ｍｍ以下であるとともに、中心線表面粗さが１５μｍ以下にすることが記載されている。しかし、特許文献１で規定されている中心線表面粗さは１５μｍ以下であるが、実施例にて得られている該中心線表面粗さは６〜１３μｍという大きな値のものなので、得られる成形体の印刷性は未だ不十分なものであった。 On the other hand, as a technique for reducing the surface roughness of the molded body, for example, there is one disclosed in Japanese Patent Laid-Open No. 9-272165 (Patent Document 1). Patent Document 1 describes that the amount of compressive deformation after secondary foaming is 0.5 mm or less and the center line surface roughness is 15 μm or less so that the density of the laminated foam sheet is minimized. ing. However, although the centerline surface roughness specified in Patent Document 1 is 15 μm or less, the centerline surface roughness obtained in the examples has a large value of 6 to 13 μm, so that the obtained molding is obtained. The printability of the body was still insufficient.
特許文献１の技術を改良するものとして、特開２００１−１２９９３９号公報（特許文献２）に開示された技術がある。特許文献２には、加熱成形によって得られたポリスチレン系樹脂発泡積層体容器において、印刷が施される面の中心線表面粗さＲａ、発泡部の発泡体密度ρ、およびセルのアスペクト比Ｒから求められる印刷性特性Ｐを特定範囲に制御することが記載されている。しかし、特許文献２には、印刷性に優れた容器の特性は記載されていても、いかなる積層発泡シートを用いれば該容器を得ることができるかについては十分に記載されておらず、特別な積層発泡シートを使用して通常の加熱成形をすることにより該容器が得られるのか、或いは、通常の積層発泡シートを使用して特別な加熱成形をすることにより該容器が得られるのか、製造方法について不明である。従って、印刷性に優れた容器を得ることができる積層発泡シートを開発するという観点から評価した場合、特許文献２の技術は未だ未完成な技術である。 As a technique for improving the technique of Patent Document 1, there is a technique disclosed in Japanese Patent Laid-Open No. 2001-129939 (Patent Document 2). In Patent Document 2, in a polystyrene resin foam laminate container obtained by thermoforming, from the center line surface roughness Ra of the surface to be printed, the foam density ρ of the foamed portion, and the cell aspect ratio R It describes that the required printability characteristic P is controlled within a specific range. However, Patent Document 2 does not fully describe what laminated foam sheet can be used to obtain the container even if the characteristics of the container excellent in printability are described. Whether the container can be obtained by ordinary thermoforming using a laminated foam sheet, or whether the container can be obtained by special thermoforming using an ordinary laminated foam sheet, production method Is unknown. Therefore, when evaluated from the viewpoint of developing a laminated foam sheet capable of obtaining a container having excellent printability, the technique of Patent Document 2 is still an incomplete technique.
本発明は、表面平滑性に優れる良好な成形体を得ることができる加熱成形条件範囲が広く、印刷ぬけ等の印刷不良が発生することのない成形体を成形可能な積層発泡シートを提供することを目的とする。 The present invention provides a laminated foamed sheet capable of forming a molded article that has a wide range of thermoforming conditions that can provide a good molded article having excellent surface smoothness and that does not cause printing defects such as printing failure. With the goal.
本発明者等は、加熱成形時における積層発泡シートの挙動を観察した結果、加熱初期は表面粗さが大きく外観が悪くなるが、更に加熱すると徐々に表面粗さが小さくなることを見出し、この知見に基づいて、二次発泡厚みの変化を緩やかにし、ヤケの発生を防止すると共に、二次発泡厚みの変化と表面粗さの変化を同期させることに想到し、本発明に到達した。尚、本明細書におけるヤケとは、シート加熱の際に過加熱によって表面が粗くざらついている状態、或いは、半溶融化しケロイド状になっている状態を言う。
本発明によれば、以下に示すポリスチレン系樹脂積層発泡シートが提供される。
〔１〕 見掛け密度が０．０８〜０．２０ｇ／ｃｍ３のポリスチレン系樹脂発泡層と該発泡層の少なくとも片面に設けられている坪量５０〜１８０ｇ／ｍ２のポリスチレン系樹脂層とからなる、厚みｈが１．５〜３．０ｍｍのポリスチレン系樹脂積層発泡シートであって、該積層発泡シートを１４５℃の加熱温度条件にて加熱時間を変化させて二次発泡させた場合に、下記条件式（１）を満足する二次発泡厚みｔ（ｍｍ）を示す全ての二次発泡後の該積層発泡シートのポリスチレン系樹脂層表面の中心線表面粗さが０．１〜１．２μｍであることを特徴とするポリスチレン系樹脂積層発泡シート。
Ｔ−０．２５ｈ ≦ ｔ ≦ Ｔ （１）
（但し、Ｔは該積層発泡シートの最大二次発泡厚み（ｍｍ）、ｔは最大二次発泡厚みＴ（ｍｍ）に達するまでの該積層発泡シートの二次発泡厚み（ｍｍ）である。）
〔２〕 該積層発泡シート中のブタン残存量が１．５０〜２．２０重量％であることを特徴とする前記〔１〕に記載のポリスチレン系樹脂積層発泡シート。
〔３〕 該ポリスチレン系樹脂発泡層における厚み方向の気泡径が５〜７０μｍの気泡の平均気泡数が、ポリスチレン系樹脂発泡層とポリスチレン系樹脂層との界面から厚み方向に２００μｍまでの範囲において４０〜６０００個／ｍｍ２であることを特徴とする前記〔１〕又は〔２〕に記載のポリスチレン系樹脂積層発泡シート。
〔４〕 該積層発泡シートの１４５℃、４０秒の加熱条件における、押出方向の加熱後寸法（Ａ）と幅方向の加熱後寸法（Ｂ）との比（Ａ）／（Ｂ）が０．９０〜１．１０であることを特徴とする前記〔１〕〜〔３〕のいずれかに記載のポリスチレン系樹脂積層発泡シート。
As a result of observing the behavior of the laminated foamed sheet at the time of heat forming, the present inventors have found that the surface roughness is large and the appearance is deteriorated at the initial stage of heating, but the surface roughness is gradually reduced by further heating. Based on the knowledge, the inventors arrived at the present invention by contemplating to moderate the change in secondary foam thickness to prevent the occurrence of burns and to synchronize the change in secondary foam thickness and the change in surface roughness. In addition, the discoloration in the present specification refers to a state where the surface is rough and rough due to overheating during sheet heating, or a state where the surface is semi-molten and keloid.
According to the present invention, the following polystyrene-based resin laminated foam sheet is provided.
[1] A polystyrene resin foam layer having an apparent density of 0.08 to 0.20 g / cm 3 and a polystyrene resin layer having a basis weight of 50 to 180 g / m 2 provided on at least one surface of the foam layer. , When the thickness h is a polystyrene-based resin laminated foam sheet having a thickness of 1.5 to 3.0 mm, and when the laminated foam sheet is subjected to secondary foaming by changing the heating time under a heating temperature condition of 145 ° C., The center line surface roughness of the surface of the polystyrene-based resin layer of the laminated foamed sheet after secondary foaming showing the secondary foaming thickness t (mm) satisfying conditional expression (1) is 0.1 to 1.2 μm. A polystyrene-based resin-laminated foam sheet characterized by being.
T−0.25h ≦ t ≦ T (1)
(However, T is the maximum secondary foam thickness (mm) of the laminated foam sheet, and t is the secondary foam thickness (mm) of the laminate foam sheet until the maximum secondary foam thickness T (mm) is reached.)
[2] The polystyrene-based resin laminated foam sheet according to [1], wherein the butane residual amount in the laminated foam sheet is 1.50 to 2.20% by weight.
[3] The average number of bubbles having a bubble diameter in the thickness direction of 5 to 70 μm in the polystyrene resin foam layer is 40 in the range from the interface between the polystyrene resin foam layer and the polystyrene resin layer to 200 μm in the thickness direction. polystyrene-based resin laminate foam sheet according to the above [1] or [2], wherein the 6000 pieces is / mm 2.
[4] When the laminated foam sheet is heated at 145 ° C. for 40 seconds, the ratio (A) / (B) of the dimension after heating (A) in the extrusion direction to the dimension after heating (B) in the width direction is 0. It is 90-1.10, The polystyrene-type resin laminated foam sheet in any one of said [1]-[3] characterized by the above-mentioned.
本発明の請求項１に係わる発明によれば、加熱成形（以下、単に熱成形ともいう。）時の加熱成形条件範囲が広く加熱成形が容易であると共に、その加熱成形条件範囲において樹脂層表面粗さが小さく調整され、得られた成形体を印刷しても、特に加熱成形直後に印刷しても、印刷ぬけ等の印刷不良が発生することがない積層発泡シートが提供される。
また、本発明の請求項２〜４に係わる発明によれば、更に優れた成形性および印刷性を有する積層発泡シートが提供される。
According to the invention relating to claim 1 of the present invention, the range of the thermoforming conditions at the time of thermoforming (hereinafter, also simply referred to as thermoforming) is wide and easy to thermoform, and the resin layer surface in the thermoforming condition range. Roughness is adjusted to be small, and a laminated foam sheet is provided that does not cause printing defects such as printing failure even when the obtained molded body is printed, particularly when printed immediately after heat molding.
Moreover, according to the invention concerning Claims 2-4 of this invention, the laminated foam sheet which has the further outstanding moldability and printability is provided.
以下、本発明のポリスチレン系樹脂積層発泡シートについて詳細に説明する。
本発明の積層発泡シートは、ポリスチレン系樹脂発泡層（以下、単に発泡層ともいう。）と該発泡層の少なくとも片面に積層されたポリスチレン系樹脂層（以下、単に樹脂層ともいう。）とからなる。
本発明の発泡層の見掛け密度は０．０８〜０．２０ｇ／ｃｍ３であり、０．０９〜０．２０ｇ／ｃｍ３が好ましく、更に０．１１〜０．２０ｇ／ｃｍ３が好ましく、特に０．１３〜０．１９ｇ／ｃｍ３が好ましい。見掛け密度が低すぎると、得られる成形体の保形性や天地圧縮強度等の機械的強度が低くなる虞がある。見掛け密度が高すぎると、断熱性が低くなる虞や、コストが高くなる虞がある。
Hereinafter, the polystyrene resin laminated foam sheet of the present invention will be described in detail.
The laminated foam sheet of the present invention comprises a polystyrene resin foam layer (hereinafter also simply referred to as a foam layer) and a polystyrene resin layer (hereinafter also simply referred to as a resin layer) laminated on at least one surface of the foam layer. Become.
Apparent density of the foamed layer of the present invention is 0.08~0.20g / cm 3, preferably 0.09~0.20g / cm 3, preferably more 0.11~0.20g / cm 3, particularly 0.13 to 0.19 g / cm 3 is preferable. If the apparent density is too low, there is a possibility that the mechanical strength such as shape retention and vertical compression strength of the obtained molded product is lowered. If the apparent density is too high, there is a possibility that the heat insulating property is lowered and the cost is increased.
上記発泡層を構成するポリスチレン系樹脂としては、ポリスチレン、スチレン−アクリロニトリル共重合体、スチレン−ブタジエン共重合体、スチレン−アクリル酸メチル共重合体、スチレン−メタクリル酸メチル共重合体、スチレン−アクリル酸共重合体、スチレン−メタクリル酸共重合体、スチレン−無水マレイン酸共重合体、ポリメチルスチレン、ポリスチレンとポリフェニレンエーテルとの混合物などが挙げられる。 Examples of the polystyrene resin constituting the foam layer include polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-methyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-acrylic acid. Examples thereof include a copolymer, a styrene-methacrylic acid copolymer, a styrene-maleic anhydride copolymer, polymethylstyrene, and a mixture of polystyrene and polyphenylene ether.
本発明の積層発泡シートにおいては、上記発泡層の少なくとも片面に坪量５０〜１８０ｇ／ｍ２のポリスチレン系樹脂層が形成されている。該坪量が５０ｇ／ｍ２未満の場合は、樹脂層が薄すぎて成形体の機械的強度や印刷適性を向上させるという効果が十分に得られない虞がある。この観点から、該坪量は９０ｇ／ｍ２以上が好ましく、１００ｇ／ｍ２以上がより好ましい。一方、該坪量が１８０ｇ／ｍ２を超える場合は、過剰な剛性となり、コストも高いものとなる虞れがある。この観点から、該坪量は１５０ｇ／ｍ２以下が好ましく、１３０ｇ／ｍ２以下がより好ましい。 In the laminated foam sheet of the present invention, a polystyrene resin layer having a basis weight of 50 to 180 g / m 2 is formed on at least one surface of the foam layer. When the basis weight is less than 50 g / m 2 , the resin layer is too thin, and there is a possibility that the effect of improving the mechanical strength and printability of the molded article may not be sufficiently obtained. From this viewpoint, the basis weight is preferably 90 g / m 2 or more, and more preferably 100 g / m 2 or more. On the other hand, when the basis weight exceeds 180 g / m 2 , the rigidity becomes excessive and the cost may be high. In this respect,該坪weight is preferably 150 g / m 2 or less, more preferably 130 g / m 2 or less.
上記樹脂層は発泡層を構成するポリスチレン系樹脂と同様のものを使用することができる。更に、耐衝撃性に優れたものとなる点から、スチレン成分とゴム成分とからなり、両者の総和を１００重量％とした場合、スチレン成分６５〜９８重量％、ゴム成分３５〜２重量％とからなるポリスチレン系樹脂が好ましい。具体的には例えば次のものが挙げられる。
（１）スチレン成分とゴム成分とからなるランダム共重合体樹脂、ブロック共重合体樹脂、グラフト共重合体樹脂、又はこれら共重合体樹脂の２種以上の混合物。
（２）上記（１）の樹脂とスチレン単独重合体との混合物。
（３）スチレン単独重合体とゴム（熱可塑性エラストマーも含む）との混合物。
（４）上記（１）の樹脂又は（２）の樹脂と、ゴム（熱可塑性エラストマーも含む）との混合物。
なお、樹脂層を構成する樹脂としては、積層発泡シート及びその成形体への耐衝撃性付与並びに強度付与の観点から、シャルピー衝撃強さＪＩＳ Ｋ７１１１（１９９６年）において方法の分類をＩＳＯ１７９／１ｅＡとしてその値が３〜２０ｋＪ／ｍ２、好ましくは６〜１６ｋＪ／ｍ２のものを使用することが好ましい。
The said resin layer can use the thing similar to the polystyrene-type resin which comprises a foaming layer. Furthermore, from the point which becomes the thing excellent in impact resistance, when it consists of a styrene component and a rubber component and the sum total of both is 100 weight%, 65-98 weight% of styrene components, 35-2 weight% of rubber components, A polystyrene-based resin is preferable. Specific examples include the following.
(1) A random copolymer resin comprising a styrene component and a rubber component, a block copolymer resin, a graft copolymer resin, or a mixture of two or more of these copolymer resins.
(2) A mixture of the resin of (1) above and a styrene homopolymer.
(3) A mixture of styrene homopolymer and rubber (including thermoplastic elastomer).
(4) A mixture of the resin (1) or the resin (2) and rubber (including a thermoplastic elastomer).
The resin constituting the resin layer is classified as ISO 179 / 1eA in the Charpy impact strength JIS K7111 (1996) from the viewpoint of imparting impact resistance and strength to the laminated foam sheet and its molded product. It is preferable to use those having a value of 3 to 20 kJ / m 2 , preferably 6 to 16 kJ / m 2 .
また、上記樹脂層は、深絞り成形性に優れていることから、無延伸のものが好ましい。 Moreover, since the said resin layer is excellent in deep drawing moldability, the non-stretched thing is preferable.
本発明の積層発泡シートの厚み（以下、一次厚みともいう。）ｈは１．５〜３．０ｍｍであり、１．９〜２．９ｍｍが好ましく、２．０〜２．８ｍｍがより好ましい。該一次厚みｈが１．５ｍｍ未満の場合、厚みが薄すぎて深絞り成形ができない虞や、得られる成形体に熱湯を入れた場合、変形する虞がある。一方、該一次厚みｈが３．０ｍｍを超える場合、熱成形時にナキや中割れの成形不良が発生する虞がある。 The thickness (hereinafter also referred to as primary thickness) h of the laminated foam sheet of the present invention is 1.5 to 3.0 mm, preferably 1.9 to 2.9 mm, and more preferably 2.0 to 2.8 mm. When the primary thickness h is less than 1.5 mm, the thickness may be too thin to perform deep drawing, or when hot water is added to the resulting molded body, it may be deformed. On the other hand, when the primary thickness h exceeds 3.0 mm, there is a possibility that a molding defect such as a crack or a middle crack may occur during thermoforming.
上記ナキとは、厚みが厚すぎる場合や発泡シートの熱成形時の伸びが不充分なことに起因して起こる現象で、得られた成形体の口縁部付近の周壁に亀裂が発生することをいい、また中割れとは、ナキと同様の理由により得られた成形体の側面部に亀裂が発生することをいう。これらナキや中割れが発生した成形体は商品として価値がないものである。 Naki is a phenomenon that occurs when the thickness is too thick or when the foamed sheet is not sufficiently stretched during thermoforming, and cracks occur in the peripheral wall near the lip of the resulting molded body. In addition, the term “medium crack” means that a crack is generated in the side surface portion of the molded product obtained for the same reason as that of naki. The molded body in which such cracks and cracks are generated is not valuable as a product.
本発明の積層発泡シートは、該積層発泡シートを加熱することにより二次発泡して厚みを増す。そして、１４５℃の加熱温度条件による二次発泡により厚みを増した積層発泡シートの厚み（以下、二次発泡厚みという。）ｔ（ｍｍ）が下記条件式（１）にて示される全範囲内において、該積層発泡シートの樹脂層表面の中心線表面粗さが０．１〜１．２μｍとなっているものである。
Ｔ−０．２５ｈ≦ｔ≦Ｔ （１）
但し、Ｔは該積層発泡シートを最も厚く二次発泡させた際の該積層発泡シートの二次発泡厚み（以下、最大二次発泡厚みと言う。）（ｍｍ）、ｔは最大二次発泡厚みＴ（ｍｍ）に達するまでの該積層発泡シートの二次発泡厚み（ｍｍ）である。また、ｈは加熱前の積層発泡シートの厚み、即ち一次厚み（ｍｍ）である。
The laminated foamed sheet of the present invention is secondarily foamed by heating the laminated foamed sheet to increase the thickness. And the thickness (henceforth a secondary foam thickness) t (mm) of the laminated foam sheet which increased thickness by the secondary foaming by 145 degreeC heating temperature conditions is in the full range shown by the following conditional expression (1). The center line surface roughness of the resin layer surface of the laminated foam sheet is from 0.1 to 1.2 μm.
T−0.25h ≦ t ≦ T (1)
However, T is the secondary foam thickness (hereinafter referred to as the maximum secondary foam thickness) of the laminated foam sheet when the laminated foam sheet is secondarily foamed (hereinafter referred to as the maximum secondary foam thickness) (mm), and t is the maximum secondary foam thickness. The secondary foaming thickness (mm) of the laminated foamed sheet until T (mm) is reached. H is the thickness of the laminated foam sheet before heating, that is, the primary thickness (mm).
上記条件式（１）で示される二次発泡厚みｔの範囲は、例えば、丼成形用の積層発泡シートの場合、通常一次厚みｈが２ｍｍ、最大二次発泡厚みＴが５．２ｍｍであることから、４．７≦ｔ≦５．２となる。この条件式（１）で示される範囲は、好ましく熱成形を行なうことができる二次発泡厚みの範囲を表し、条件式（１）で示される全ての範囲で、中心線表面粗さ（以下、単に表面粗さともいう。）が０．１〜１．２μｍであることは、中心線表面粗さが加熱成形可能な全ての範囲で小さいことを意味し、これらの要件を満たす積層発泡シートは印刷ぬけ等の印刷不良が発生することがなく、特に加熱成形直後の印刷不良が発生し易い状態の成形体に対しても有効に印刷不良発生を抑制することができる。 The range of the secondary foam thickness t shown by the conditional expression (1) is, for example, in the case of a laminated foam sheet for forming a cocoon, the primary thickness h is usually 2 mm and the maximum secondary foam thickness T is 5.2 mm. Therefore, 4.7 ≦ t ≦ 5.2. The range represented by this conditional expression (1) represents the range of the secondary foam thickness that can be preferably thermoformed, and the center line surface roughness (hereinafter, A surface roughness of 0.1 to 1.2 μm means that the center line surface roughness is small in the entire range that can be thermoformed, and a laminated foam sheet that satisfies these requirements is Printing defects such as printing defects do not occur, and the occurrence of printing defects can be effectively suppressed even for a molded body in a state where printing defects are likely to occur immediately after heat molding.
本明細書において、上記積層発泡シートの１４５℃での加熱は、積層発泡シートの厚みはそのままとして該積層発泡シートから、縦、横のそれぞれの辺が、発泡層の押出方向、幅方向と一致するようにして、一辺２６０ｍｍの正方形サンプルを切り出して行なうものとする。具体的には、次のように行う。
積層発泡シートの厚みはそのままとして積層発泡シートから、縦、横のそれぞれの辺が、発泡層の押出方向、幅方向と一致するようにして、一辺２６０ｍｍの正方形サンプルを切り出す。
次に、縦２００ｍｍ、横２００ｍｍの正方形の窓部を有する２枚の木枠間に該サンプルを挟み込む。
In this specification, heating the laminated foam sheet at 145 ° C. means that the thickness of the laminated foam sheet remains as it is, and the vertical and horizontal sides of the laminated foam sheet coincide with the extrusion direction and the width direction of the foam layer. In this manner, a square sample having a side of 260 mm is cut out. Specifically, this is performed as follows.
A square sample having a side of 260 mm is cut out from the laminated foam sheet with the thickness of the laminated foam sheet as it is so that the longitudinal and lateral sides coincide with the extrusion direction and the width direction of the foam layer.
Next, the sample is sandwiched between two wooden frames having square windows of 200 mm length and 200 mm width.
かかる状態に木枠間に保持された積層発泡シートサンプルを、１４５℃に温度調節された空気循環式オーブン（例えば、タバイエスペック株式会社製 品番PERFECT OVEN ＰＨ−２００）に入れて所定時間加熱した後、オーブンから取り出して２５℃の温度条件下に放置して冷却して二次発泡した積層発泡シートを得る。なお、上記所定時間の加熱は、３秒間、６秒間、９秒間、１２秒間，１５秒間、１８秒間、２１秒間、２４秒間、２７秒間、３０秒間、３３秒間、３６秒間、更に、必要に応じて順次プラス３秒間の３秒毎とし、得られた各々の加熱後のサンプルの二次発泡厚み及び中心線表面粗さのデータに基づき図１に示すグラフを得ることができる。尚、上記測定は、サンプルにヤケが発生し二次発泡厚みの低下が確認されるまで行う。
また、上記測定において加熱条件を１４５℃としたのは、積層発泡シートの加熱炉を使用した成形体の連続生産における熱成形時の挙動を、空気循環式オーブンにて再現する上で好適な条件であるためである。
The laminated foam sheet sample held between the wooden frames in such a state is placed in an air circulation oven (eg, product number PERFECT OVEN PH-200 manufactured by Tabai Espec Co., Ltd.) whose temperature is adjusted to 145 ° C. and heated for a predetermined time. Then, it is taken out from the oven, left under a temperature condition of 25 ° C. and cooled to obtain a secondary foamed laminated foam sheet. In addition, the heating for the predetermined time is 3 seconds, 6 seconds, 9 seconds, 12 seconds, 15 seconds, 18 seconds, 21 seconds, 24 seconds, 27 seconds, 30 seconds, 33 seconds, 36 seconds, and further if necessary. Then, the graph shown in FIG. 1 can be obtained on the basis of the data of the secondary foaming thickness and the center line surface roughness of each of the obtained samples after heating. The above measurement is performed until the sample is burned and a decrease in the secondary foam thickness is confirmed.
In the above measurement, the heating condition was set to 145 ° C. because the behavior at the time of thermoforming in the continuous production of a molded body using a heating furnace for a laminated foam sheet was suitable for reproducing in an air circulation oven. This is because.
上記中心線表面粗さの下限値は、０．１μｍ未満でも構わないが、概ね本発明の目的、効果を達成する上で、積層発泡シートの中心線表面粗さとして、０．１μｍ程度以上であれば十分な効果が見込まれることによるものである。一方、上記中心線表面粗さが１．２μｍを超えると、金型加熱成形により得られた成形体は、印刷抜けが発生する虞がある。 The lower limit of the centerline surface roughness may be less than 0.1 μm, but in order to achieve the objects and effects of the present invention, the centerline surface roughness of the laminated foam sheet is about 0.1 μm or more. This is because sufficient effects are expected. On the other hand, if the surface roughness of the center line exceeds 1.2 μm, the molded product obtained by the mold heat molding may cause printing omission.
本明細書における発泡層の見掛け密度、一次厚みｈ、樹脂層の坪量等は次の方法に従って測定される。
まず、本発明の積層発泡シートから、積層発泡シートの押出方向と一致する方向に５０ｃｍ、且つ積層発泡シートの幅方向と一致する方向に５０ｃｍの正方形のサンプルを切り出す。尚、この際、幅方向の中央部とサンプル中央部が一致するようにする。
In this specification, the apparent density of the foam layer, the primary thickness h, the basis weight of the resin layer, and the like are measured according to the following methods.
First, from the laminated foam sheet of the present invention, a square sample of 50 cm is cut out in a direction coinciding with the extrusion direction of the laminated foam sheet and 50 cm in a direction coinciding with the width direction of the laminated foam sheet. At this time, the central portion in the width direction is made to coincide with the central portion of the sample.
次に、サンプルの幅方向のいずれか一方の垂直断面において、片方の端部を基準として５ｃｍ間隔で他方の端部に至るまでの幅方向両端部を除く合計９箇所の測定点について、積層発泡シートの一次厚みｈと発泡層の厚みを、顕微鏡で撮影した写真に基づいて測定する。 Next, in any one of the vertical cross sections in the width direction of the sample, a total of nine measurement points excluding both end portions in the width direction from the one end portion to the other end portion at intervals of 5 cm are laminated and foamed. The primary thickness h of the sheet and the thickness of the foam layer are measured based on a photograph taken with a microscope.
上記９箇所の測定点の測定値を相加平均することにより、積層発泡シートの一次厚みｈ（ｍｍ）と発泡層の厚み（ｍｍ）を求める。また、積層発泡シートの一次厚みｈから上記発泡層の厚み（ｍｍ）を引くことによって得られる値をもって、樹脂層の厚み（ｍｍ）とする。 The primary thickness h (mm) of the laminated foamed sheet and the thickness (mm) of the foamed layer are obtained by arithmetically averaging the measured values at the nine measurement points. The value obtained by subtracting the thickness (mm) of the foamed layer from the primary thickness h of the laminated foamed sheet is defined as the thickness (mm) of the resin layer.
また、上記サンプルの重量（ｇ）を測定し、その測定値を１ｍ２当たりの積層発泡シートの重量に換算して積層発泡シートの坪量（ｇ／ｍ２）とする。樹脂層の１ｍ２当たりの重量（ｇ）である樹脂層の坪量（ｇ／ｍ２）は、樹脂層の密度、即ち樹脂層の基材樹脂の密度に上記樹脂層の厚みを掛算し単位に変換することによって求められる。また、発泡層の１ｍ２当たりの重量である発泡層の坪量（ｇ／ｍ２）は、積層発泡シートの坪量（ｇ／ｍ２）から樹脂層の坪量（ｇ／ｍ２）を引算することによって求められる。 Moreover, the weight (g) of the said sample is measured, The measured value is converted into the weight of the laminated foam sheet per 1 m < 2 >, and it is set as the basic weight (g / m < 2 >) of a laminated foam sheet. The basis weight of the resin layer is the weight of 1 m 2 per resin layer (g) (g / m 2 ) , the density of the resin layer, i.e., the density of the base resin of the resin layer of the resin layer by multiplying the thickness units Is obtained by converting to The basis weight of the weight of 1 m 2 per foam layer foamed layer (g / m 2) of basis weight of the laminated foam sheet basis weight of (g / m 2) from the resin layer (g / m 2) It is obtained by subtraction.
発泡層の見掛け密度は上記発泡層の坪量（ｇ／ｍ２）を上記発泡層の厚みにて割り算し単位に変換することによって求められる。 The apparent density of the foam layer is determined by dividing the basis weight (g / m 2 ) of the foam layer by the thickness of the foam layer and converting it into units.
また、本発明における二次発泡厚みは、加熱冷却後のサンプルの固定枠内側窓部に位置する二次発泡した部分の図２に示す点Ａ〜Ｉの合計９箇所の測定点について、積層発泡シートの二次発泡厚みを、垂直断面の顕微鏡写真に基づき測定する。そして上記９箇所の測定点の測定値を相加平均することにより、積層発泡シートの二次発泡厚み（ｍｍ）を算出する。
また、最大二次発泡厚みは、図１のように得られる二次発泡厚みと加熱時間との関係を示す曲線の二次発泡厚みの最大値をその値とする。
In addition, the secondary foam thickness in the present invention is the laminated foam at the measurement points of a total of nine points A to I shown in FIG. 2 of the secondary foam portion located in the fixed frame inner window portion of the sample after heating and cooling. The secondary foam thickness of the sheet is measured based on a micrograph of a vertical cross section. Then, the secondary foam thickness (mm) of the laminated foam sheet is calculated by arithmetically averaging the measurement values at the nine measurement points.
Further, the maximum secondary foam thickness is the maximum value of the secondary foam thickness of the curve showing the relationship between the secondary foam thickness and the heating time obtained as shown in FIG.
本発明における積層発泡シートの樹脂層表面の中心線表面粗さは、表面粗さ計を用いてＪＩＳ−Ｂ０６０１（１９９４）に準じて測定する。表面粗さ計としては一般に使用されているものでよく、例えば、（株）小坂研究所製のサーフコーダＳＥ−３ＯＤ、サーフコーダＳＥ１７００αが挙げられる。中心線表面粗さの測定は、前記測定サンプルの幅方向に沿って８ｍｍの測定距離を５回測定し、その平均値を中心線表面粗さとする。なお、測定時の計測速度は０．２５ｍｍ／秒以下で実施する。 The center line surface roughness of the resin layer surface of the laminated foam sheet in the present invention is measured according to JIS-B0601 (1994) using a surface roughness meter. As the surface roughness meter, those generally used may be used. Examples thereof include Surfcorder SE-3OD and Surfcorder SE1700α manufactured by Kosaka Laboratory. For the measurement of the center line surface roughness, a measurement distance of 8 mm is measured five times along the width direction of the measurement sample, and the average value is defined as the center line surface roughness. The measurement speed at the time of measurement is 0.25 mm / second or less.
次に、図１に基づき、従来の積層発泡シートと対比しながら、上記本発明の特徴について具体的に説明する。図１は、加熱温度一定の条件における、加熱時間（横軸）に対する二次発泡厚みｔ（左の縦軸）、中心線表面粗さ（右の縦軸）の変化を表すグラフであり、実線が本発明の積層発泡シート、破線が従来の積層発泡シートである。
但し、図１には、本発明の実施例の一例として、一次厚みｈが２．３ｍｍ、最大二次発泡厚みＴが５．４ｍｍの積層発泡シートについて示すが、本発明はこれに限定されるものではない。
Next, based on FIG. 1, the features of the present invention will be specifically described in comparison with a conventional laminated foam sheet. FIG. 1 is a graph showing changes in secondary foam thickness t (left vertical axis) and centerline surface roughness (right vertical axis) with respect to heating time (horizontal axis) under a constant heating temperature, and a solid line Is a laminated foam sheet of the present invention, and a broken line is a conventional laminated foam sheet.
However, FIG. 1 shows a laminated foam sheet having a primary thickness h of 2.3 mm and a maximum secondary foam thickness T of 5.4 mm as an example of the embodiment of the present invention, but the present invention is limited to this. It is not a thing.
本発明の積層発泡シートにおいては、図１に示すように、二次発泡厚みｔが緩やかに増加し、しかも二次発泡厚みｔが（Ｔ−０．２５ｈ）に達する付近から略一定の値となって、ヤケが発生することなく最大二次発泡厚みＴに徐々に近づいて行く。これに対し、従来の積層発泡シートにおいては、二次発泡厚みｔが急激に増加し、最大二次発泡厚みに達すると、間もなくヤケが発生し始めて二次発泡厚みｔは減少し二次発泡厚みの水平領域はほとんど現れていない。 In the laminated foam sheet of the present invention, as shown in FIG. 1, the secondary foam thickness t gradually increases, and the secondary foam thickness t is a substantially constant value from the vicinity where it reaches (T−0.25h). Thus, the maximum secondary foaming thickness T is gradually approached without generation of burns. On the other hand, in the conventional laminated foam sheet, the secondary foam thickness t increases rapidly, and when the maximum secondary foam thickness is reached, burns begin to occur soon and the secondary foam thickness t decreases and the secondary foam thickness decreases. There is almost no horizontal area.
本発明における二次発泡厚みｔが上記のように変化するのに対し、本発明での中心線表面粗さは、二次発泡厚みｔが（Ｔ−０．２５ｈ）に達する前に最大の値となり、それ以後は徐々に小さくなり、二次発泡厚みｔが（Ｔ−０．２５ｈ）に達してからは略一定値の水平領域となる。これに対し、従来の積層発泡シートにおいては、中心線表面粗さは、本発明のものと略同じ加熱時間で最大の値となるが、その最大値は本発明のものの最大値よりも大きく、それ以後は徐々に小さくなっても成形可能範囲における中心線表面粗さが本発明よりも大きな値となる。なお、本発明の積層発泡シートにおいて、中心線表面粗さの最大値が従来のものの該最大値よりも小さくなる理由は、シートの加熱過程においシートの収縮挙動が小さく、それに伴うシート表面の微少なうねりが小さいためであるためと考えられる。 While the secondary foam thickness t in the present invention changes as described above, the center line surface roughness in the present invention is the maximum value before the secondary foam thickness t reaches (T-0.25h). After that, it gradually decreases, and after the secondary foam thickness t reaches (T-0.25h), it becomes a horizontal region having a substantially constant value. On the other hand, in the conventional laminated foam sheet, the center line surface roughness is the maximum value in substantially the same heating time as that of the present invention, the maximum value is larger than the maximum value of the present invention, Thereafter, even if it gradually decreases, the center line surface roughness in the moldable range becomes a larger value than in the present invention. In the laminated foam sheet of the present invention, the reason why the maximum value of the centerline surface roughness is smaller than the maximum value of the conventional one is that the sheet shrinkage behavior is small during the heating process of the sheet, and the sheet surface is accompanied by a small amount. This is probably because the undulation is small.
図１に示されるように、本発明では二次発泡厚みの変化を緩やかにすることによりヤケの発生が防止され、二次発泡厚みの変化が水平に近い曲線領域（以下、二次発泡厚みの水平領域という。）が現れることにより、成形可能な加熱時間の範囲が広くなっている。更に、表面粗さの変化が緩やかになり水平に近い曲線領域（以下、表面粗さの水平領域という。）と該二次発泡厚みの水平領域とを熱成形加熱時間に対して同期させることができるので、二次発泡厚みの変化のみに着目して成形条件を設定すれば表面粗さの小さい成形体を容易に得ることができる。この構成は、本発明者等が、積層発泡シートの加熱状態について解析、検討した結果、積層発泡シートの加熱時において中心線表面粗さの最大値を小さくすることと二次発泡厚みの水平領域を形成させることとを同時に成し遂げたことによる。なお、表面粗さの微妙な変化を積層発泡シートの加熱成形時に見極めることは困難である。そこで、本発明においては表面粗さの水平領域と二次発泡厚みの水平領域とを同期させることによって、積層発泡シートの加熱成形時に見極めることが可能な二次発泡厚みの変化に着目するたけで、表面粗さの小さい状態のものであるか否かが判別でき、その結果、二次発泡厚みの水平領域にて積層発泡シートを熱成形すれば、表面粗さの小さな良好な成形体を得ることができる。 As shown in FIG. 1, in the present invention, the change in the secondary foam thickness is moderated to prevent the occurrence of burns, and the change in the secondary foam thickness is a curved region close to the horizontal (hereinafter referred to as the secondary foam thickness). The appearance of the horizontal region) increases the range of heating time that can be molded. Furthermore, the change of the surface roughness becomes gentle and the curve area close to horizontal (hereinafter referred to as the horizontal area of the surface roughness) and the horizontal area of the secondary foam thickness can be synchronized with the thermoforming heating time. Therefore, if the molding conditions are set by paying attention only to the change in the secondary foam thickness, a molded body having a small surface roughness can be easily obtained. As a result of the present inventors analyzing and examining the heating state of the laminated foam sheet, the present inventors reduced the maximum value of the center line surface roughness during heating of the laminated foam sheet and the horizontal region of the secondary foam thickness. It is because it was accomplished at the same time to form. It should be noted that it is difficult to ascertain subtle changes in surface roughness during the heat forming of the laminated foam sheet. Therefore, in the present invention, by synchronizing the horizontal region of the surface roughness and the horizontal region of the secondary foam thickness, it is only necessary to pay attention to the change in the secondary foam thickness that can be determined during the heat forming of the laminated foam sheet. It is possible to determine whether the surface roughness is low or not, and as a result, if the laminated foam sheet is thermoformed in the horizontal region of the secondary foam thickness, a good molded body having a small surface roughness can be obtained. be able to.
積層発泡シートの表面および全体厚みは、加熱が進むにつれて次の（１）〜（４）の段階で変化する。積層発泡シートを加熱すると、まず１）発泡積層シートの樹脂層表面に凹凸が発生し同時に表面粗さが大きくなる（例えば、１４５℃の空気循環式オーブンにて再現すると図１本発明品の加熱時間２０秒付近）。次に、２）加熱により発泡がより進むにつれて樹脂層表面の凹凸が小さくなり表面粗さも小さくなり（同図１本発明品の加熱時間２０〜３０秒付近）、３）更に発泡が進むと表面粗さは更に小さくなり（同図１本発明品の加熱時間３０秒〜７５秒付近）、４）加熱され過ぎると発泡層や樹脂層にヤケが発生する（同図１本発明品の加熱時間７５秒以降）。 The surface and the overall thickness of the laminated foam sheet change in the following steps (1) to (4) as the heating proceeds. When the laminated foam sheet is heated, first, 1) unevenness is generated on the surface of the resin layer of the foam laminated sheet and the surface roughness is increased simultaneously (for example, when reproduced in an air circulation oven at 145 ° C., FIG. Time around 20 seconds). Next, 2) As the foaming progresses further by heating, the unevenness of the surface of the resin layer becomes smaller and the surface roughness also becomes smaller (Fig. 1, the heating time of the product of the present invention is around 20 to 30 seconds). The roughness becomes even smaller (the heating time of the product of the present invention in FIG. 1 is about 30 seconds to 75 seconds), 4) burns occur in the foam layer and the resin layer if heated too much (heating time of the product of the present invention in FIG. After 75 seconds).
発泡積層シートを加熱すると、その表面状態は前述したように１）〜４）の段階からなり、表面粗さが小さな成形体を得るには３）の段階で前記条件式（１）を満足する二次発泡厚みｔを保持している加熱軟化状態の発泡積層シートを成形する必要がある。そして、本発明の発泡積層シートは、上記の表面粗さが小さな成形体を得るために必要な状態を維持している時間が長いものである。 When the foamed laminated sheet is heated, the surface state thereof consists of the steps 1) to 4) as described above, and the conditional expression (1) is satisfied in the step 3) to obtain a molded product having a small surface roughness. It is necessary to form a foamed laminated sheet in a heat-softened state that maintains the secondary foam thickness t. And the foaming lamination sheet of this invention has a long time maintaining the state required in order to obtain a molded object with said small surface roughness.
本発明の積層発泡シートにおいては、発泡剤として少なくとも５０モル％以上のブタンを含むものを用いることが好ましく、その場合は積層発泡シート中のブタン残存量が１．５０〜２．２０重量％であることが好ましく、１．５０〜２．１０重量％がより好ましく、１．６０〜２．００重量％が更に好ましい。
ブタン残存量が目的とする二次発泡厚みとの関係において少なすぎる場合には、前記３）の段階に至るためにシートに過多な熱量を与える必要がありヤケなどの不具合の虞がある。一方、ブタン残存量が目的とする二次発泡厚みとの関係において多すぎる場合には、二次発泡厚みｔが急激に増加して図１に示すような二次発泡厚みにおける水平領域が得られず、ナキやヤケなどの成形不具合を引き起こす虞がある。
本明細書におけるブタン残存量の測定は、積層発泡シートから採取した短冊状の測定試料を、トルエンを入れた蓋付の試料ビンの中に入れ、撹拌して積層発泡シート中のブタンをトルエンに溶解させた後、ブタンを溶解したトルエンをマイクロシリンジで採取してガスクロマトグラフィー分析にかけて、内部標準法により求めることができる。
In the laminated foam sheet of the present invention, it is preferable to use a foaming agent containing at least 50 mol% or more of butane. In that case, the residual amount of butane in the laminated foam sheet is 1.50 to 2.20% by weight. Preferably, it is 1.50 to 2.10% by weight, more preferably 1.60 to 2.00% by weight.
If the amount of butane remaining is too small in relation to the desired secondary foam thickness, it is necessary to apply an excessive amount of heat to the sheet to reach the stage 3), which may cause problems such as burns. On the other hand, if the amount of butane remaining is too large in relation to the desired secondary foam thickness, the secondary foam thickness t increases rapidly, and a horizontal region in the secondary foam thickness as shown in FIG. 1 is obtained. However, there is a risk of causing molding defects such as cracks and burns.
In this specification, the amount of butane remaining is measured by placing a strip-shaped measurement sample taken from a laminated foam sheet into a sample bottle with a lid containing toluene and stirring the butane in the laminated foam sheet into toluene. After dissolution, toluene in which butane is dissolved can be collected by a microsyringe and subjected to gas chromatography analysis, which can be determined by an internal standard method.
また、本発明の積層発泡シートを構成する発泡層においては、発泡層と樹脂層との界面から厚み方向に２００μｍまでの範囲（以下、発泡層表層部ともいう。）における厚み方向の気泡径が５〜７０μｍの気泡の平均気泡数が、４０〜６０００個／ｍｍ２、更に２５０〜６０００個／ｍｍ２、更に５００〜５０００個／ｍｍ２、特に１０００〜４０００個／ｍｍ２であることが好ましい。なお、この場合、発泡層表層部の全気泡数に対して該気泡径が５〜７０μｍの気泡の平均気泡数が５０％以上、更に７０％以上、特に８５％以上であることが好ましい。該気泡径が５〜７０μｍの気泡の平均気泡数が上記範囲内であれば、従来の積層発泡シートにおいては熱成形時においてヤケ等の発生が懸念されるが、本発明のものはそのような心配はなく、得られる成形体の加熱成形直後における印刷性が更に良好になる等の優れた効果を有するものとなる。なお、該気泡径が５〜７０μｍの気泡の平均気泡数の調整方法としては、例えば、発泡シートの押出発泡成形時に押出直後の発泡シート表面をエアーなどで急冷し気泡の発生を抑制すると共に樹脂層を積層接着する際の熱接着温度を通常よりも低く設定する方法や、発泡シート表面をエアーなどで急冷し気泡の発生を抑制すると共に樹脂層を積層接着する前に発泡シートを微細セルが形成され無い程度の温度に調整された加熱ロール間に通して、発泡シート表面に含有されている発泡剤を揮散させて発泡剤含有量を低下させた後に通常の温度で樹脂層を積層接着する方法等が挙げられる。 Moreover, in the foam layer constituting the laminated foam sheet of the present invention, the cell diameter in the thickness direction in the range from the interface between the foam layer and the resin layer to 200 μm in the thickness direction (hereinafter also referred to as the foam layer surface layer portion). average cell number of bubbles 5~70μm is 40-6000 pieces / mm 2, further 250 to 6,000 pieces / mm 2, is preferably further 500 to 5,000 pieces / mm 2, in particular 1000 to 4000 pieces / mm 2 . In this case, the average number of bubbles having a bubble diameter of 5 to 70 μm is preferably 50% or more, more preferably 70% or more, and particularly preferably 85% or more with respect to the total number of bubbles in the surface portion of the foam layer. If the average cell number of the bubbles having a bubble diameter of 5 to 70 μm is within the above range, the conventional laminated foam sheet may be burned at the time of thermoforming. There is no worry, and the resulting molded article has excellent effects such as further improved printability immediately after heat molding. In addition, as an adjustment method of the average bubble number of the bubbles having a bubble diameter of 5 to 70 μm, for example, the foam sheet surface immediately after extrusion is rapidly cooled with air or the like at the time of extrusion foam molding of the foam sheet to suppress generation of bubbles and resin. The method of setting the thermal bonding temperature when laminating and laminating the layers to a lower temperature than usual, or the surface of the foam sheet is rapidly cooled with air to suppress the generation of bubbles, and before the resin layer is laminated and adhered, The resin layer is laminated and bonded at a normal temperature after the foaming agent contained in the surface of the foamed sheet is volatilized to reduce the foaming agent content by passing between heated rolls adjusted to a temperature at which it is not formed. Methods and the like.
上記平均気泡数の測定方法としては、積層発泡シートの押出方向の垂直縦断面を撮影した顕微鏡写真（倍率を２００倍）に基づき、樹脂層と発泡層との界面から発泡層側の厚さ２００μｍとそれに直交する方向に５００μｍ、即ち２００μｍ×５００μｍの範囲内に存在する気泡についてカウントし、１ｍｍ2あたりの気泡数に換算した値を平均気泡数（個／ｍｍ2）とする。なお、該平均気泡数の測定にあたっては、気泡の一部でも上記範囲に含まれている場合はカウントする。特に、気泡径が５〜７０μｍの気泡の平均気泡数測定は、上記範囲内において厚み方向の気泡径が５〜７０μｍの気泡数を全てカウントし、１ｍｍ2あたりの気泡数に換算した値を平均気泡数（個／ｍｍ2）とする。 As the method for measuring the average number of bubbles, based on a micrograph (magnification is 200 times) of a vertical longitudinal section in the extrusion direction of the laminated foam sheet, the thickness of the foam layer side from the interface between the resin layer and the foam layer is 200 μm. The number of bubbles present in a range of 500 μm, that is, 200 μm × 500 μm in a direction orthogonal to the above is counted, and the value converted into the number of bubbles per 1 mm 2 is defined as the average number of bubbles (number / mm 2 ). In the measurement of the average number of bubbles, if some of the bubbles are included in the above range, they are counted. In particular, measurement of the average number of bubbles of bubbles having a bubble diameter of 5 to 70 μm is performed by counting all the numbers of bubbles having a diameter of 5 to 70 μm in the thickness direction within the above range, and averaging the values converted to the number of bubbles per 1 mm 2. The number of bubbles (number / mm 2 ).
また、本発明の積層発泡シートにおいては、積層発泡シートの１４５℃、４０秒の加熱条件における、押出方向の加熱後寸法（Ａ）と幅方向の加熱後寸法（Ｂ）との比（Ａ）／（Ｂ）が０．９０〜１．１０であることが好ましい。
該比（Ａ）／（Ｂ）がこの範囲内であれば、前記の図１における積層発泡シートの中心線表面粗さの最大値が更に小さくなり、その結果表面粗さの水平領域の中心線表面粗さの値も小さくなるので印刷性が更に良好なものが得られ、また、深絞り成形性時においてもナキ、中割れ等の成形時の不具合の発生の心配がなく、更にドローダウンも小さくなり特に優れた成形性を示すものとなる。尚、ドローダウンとは、熱成形時に長尺な積層発泡シートの両側縁をクランプして加熱ゾーンに搬送し、該加熱ゾーンでシートの両面をヒーター加熱してシートを成形可能な状態に軟化させる際に、積層発泡シートが膨張及び自重によって垂れ下がる現象であり、積層発泡シートの加熱ムラの原因の一つで、ドローダウンが発生すると成形性が悪化する。
In the laminated foam sheet of the present invention, the ratio (A) of the dimension after heating in the extrusion direction (A) and the dimension after heating in the width direction (B) under the heating conditions of 145 ° C. and 40 seconds of the laminated foam sheet. / (B) is preferably 0.90 to 1.10.
If the ratio (A) / (B) is within this range, the maximum value of the centerline surface roughness of the laminated foam sheet in FIG. 1 is further reduced, and as a result, the centerline of the horizontal region of the surface roughness Since the surface roughness value is also small, it is possible to obtain prints with even better printability, and there is no risk of problems during molding such as cracking and cracking during deep drawing, and further drawdown is possible. It becomes small and exhibits particularly excellent moldability. In addition, the draw down means that both side edges of a long laminated foam sheet are clamped and conveyed to a heating zone at the time of thermoforming, and both sides of the sheet are heated by the heater to soften the sheet to a formable state. In this case, the laminated foam sheet hangs down due to expansion and its own weight, which is one of the causes of heating unevenness of the laminated foam sheet. When drawdown occurs, the moldability deteriorates.
該比（Ａ）／（Ｂ）の値の調整方法としては、例えば、押出方向の加熱後寸法（Ａ）は、ダイ出口の間隙を調整することによって制御することができる。具体的には、ダイ出口の間隙を大きくすることによって加熱後寸法は小さくなる傾向がある。また、ダイ内の樹脂流路の出口のテーパー角度（図３）を調整することも好ましい方法である。具体的にはテーパー角度を大きくすることによって、加熱後寸法は小さくなる傾向がある。また、幅方向の加熱後寸法（Ｂ）は、ブローアップ比を大きくすると小さくなる傾向があるので、ブローアップ比を調整することにより制御することができる。ここで、ブローアップ比とは、マンドレルの直径をダイ出口の口径で割った値をいい、通常は２．５〜４．５である。更に、押出方向の加熱後寸法（Ａ）を調整する方法として、ダイを冷却する方法が挙げられる。具体的には、ダイ温度よりも低温の冷却媒体により、ダイ外周やダイの内部に位置するダイシャフトを冷却する方法等が好ましく挙げられる。この場合の冷却媒体としては、オイルや温水などが挙げられる。 As a method for adjusting the value of the ratio (A) / (B), for example, the post-heating dimension (A) in the extrusion direction can be controlled by adjusting the gap at the die outlet. Specifically, the size after heating tends to decrease by increasing the gap at the die exit. It is also a preferred method to adjust the taper angle (FIG. 3) at the outlet of the resin flow path in the die. Specifically, the dimension after heating tends to be reduced by increasing the taper angle. Moreover, since the dimension (B) after the heating in the width direction tends to decrease as the blow-up ratio is increased, it can be controlled by adjusting the blow-up ratio. Here, the blow-up ratio refers to a value obtained by dividing the diameter of the mandrel by the diameter of the die outlet, and is usually 2.5 to 4.5. Furthermore, as a method for adjusting the dimension (A) after heating in the extrusion direction, a method for cooling the die can be mentioned. Specifically, a method of cooling the die shaft located on the outer periphery of the die or inside the die with a cooling medium having a temperature lower than the die temperature is preferable. In this case, examples of the cooling medium include oil and hot water.
本発明における１４５℃、４０秒の加熱条件での押出方向の加熱後寸法（Ａ）と幅方向の加熱後寸法（Ｂ）は、一辺２００ｍｍの正方形サンプルを用いて測定した値である。具体的には、加熱後寸法の測定は次のように行う。
積層発泡シートの厚みはそのままとして積層発泡シートから、縦、横のそれぞれの辺が、発泡層の押出方向、幅方向と一致するようにして、一辺２００ｍｍの正方形サンプルを切り出す。次に、縦３００ｍｍ以上、横３００ｍｍ以上の２枚の金網間に該サンプルを保持する。尚、金網は直径０．１の針金からなり２０ｍｍ間隔に格子が形成されているものを使用し、２枚の金網間に該サンプルを保持する際の２枚の金網の間隔は５ｍｍとする。
The post-heating dimension (A) in the extrusion direction and the post-heating dimension (B) in the width direction under heating conditions of 145 ° C. and 40 seconds in the present invention are values measured using a square sample having a side of 200 mm. Specifically, the dimensions after heating are measured as follows.
A square sample having a side of 200 mm is cut out from the laminated foam sheet with the thickness of the laminated foam sheet as it is so that the longitudinal and lateral sides coincide with the extrusion direction and the width direction of the foam layer. Next, the sample is held between two metal meshes having a length of 300 mm or more and a width of 300 mm or more. The wire mesh is made of wire having a diameter of 0.1 and has a grid formed at intervals of 20 mm. The distance between the two wire meshes when the sample is held between the two wire meshes is 5 mm.
かかる状態で金網間に保持された積層発泡シートサンプルを、１４５℃に温度調節された空気循環式オーブン（例えば、タバイエスペック株式会社製 品番ＰＥＲＦＥＣＴ ＯＶＥＮ ＰＨ−２００）に入れて４０秒加熱した後、オーブンから取り出して２５℃の温度条件下に放置して冷却する。次に、該冷却後のサンプルの各方向の中心線の長さ、即ち加熱後寸法（Ａ）、（Ｂ）を測定する。 In such a state, the laminated foam sheet sample held between the metal meshes was placed in an air circulation oven (for example, product number PERFECT OVEN PH-200 manufactured by Tabai Espec Co., Ltd.) whose temperature was adjusted to 145 ° C. and heated for 40 seconds. Remove from the oven and leave to cool at 25 ° C. Next, the length of the center line in each direction of the sample after cooling, that is, the dimensions (A) and (B) after heating are measured.
このようにして得られる押出方向の加熱後寸法（Ａ）の値は、具体的には１９０〜２０４ｍｍが好ましく、更に１９２〜２０３ｍｍであることが好ましく、特に１９４〜２０１ｍｍであることがより好ましい。 Specifically, the value of dimension (A) after heating in the extrusion direction obtained in this manner is preferably 190 to 204 mm, more preferably 192 to 203 mm, and particularly preferably 194 to 201 mm.
次に、本発明の積層発泡シートの製造方法について説明する。
まず、押出機にポリスチレン系樹脂、気泡調節剤等の各種の添加剤を押出機に供給し、加熱、溶融、混練し、更に発泡剤を圧入、混練して溶融樹脂混合物とし、溶融樹脂混合物を発泡適性温度に調整して発泡性溶融樹脂混合物とし、押出機の出口に取付けた環状ダイを通して大気中に押出して筒状に発泡させる。次に、得られた筒状発泡体を円柱状の冷却装置（マンドレル）に沿わせ引取りながら冷却すると共に切り開いてシート状の発泡層を形成する。
Next, the manufacturing method of the laminated foam sheet of this invention is demonstrated.
First, various additives such as polystyrene resin and bubble regulator are supplied to the extruder, heated, melted and kneaded, and then the foaming agent is press-fitted and kneaded to obtain a molten resin mixture. The foamable molten resin mixture is adjusted to the foaming temperature and extruded into the atmosphere through an annular die attached to the outlet of the extruder and foamed into a cylindrical shape. Next, the obtained cylindrical foam is cooled while being taken along a columnar cooling device (mandrel) and cut open to form a sheet-like foam layer.
樹脂層は、発泡層が押出後ロール状に巻き取られるまでの間に他の押出機を用いて押出ラミネーション法により積層してもよく、共押出ダイを用いて発泡性溶融樹脂混合物と樹脂層用溶融樹脂とを積層合流させてから押出すことにより形成してもよい。また、発泡層を形成してから数日後に他の押出機を用いて押出ラミネーション法により積層してもよければ、フィルムをラミネートしてもよい。上記樹脂層の形成方法の中では押出ラミネーション法が特に好ましく、坪量９０ｇ／ｍ２を超える十分な厚みの成形性に優れた無延伸の樹脂層を形成することができる。 The resin layer may be laminated by an extrusion lamination method using another extruder before the foamed layer is wound up into a roll after extrusion, and the foamable molten resin mixture and the resin layer using a coextrusion die It may be formed by extruding the molten resin for use after laminating and joining. Further, a film may be laminated if it may be laminated by an extrusion lamination method using another extruder several days after the foam layer is formed. Among the methods for forming the resin layer, the extrusion lamination method is particularly preferable, and an unstretched resin layer having a sufficient thickness exceeding a basis weight of 90 g / m 2 can be formed.
前記押出機に圧入する発泡剤としては、有機系物理発泡剤、無機系物理発泡剤等を、それぞれ単独で又は２以上組み合わせて用いられる。有機系物理発泡剤としては、例えばプロパン、ノルマルブタン、イソブタン、イソペンタン、ノルマルペンタン、ヘキサン等の脂肪族炭化水素類、シクロペンタン、シクロヘキサン等の脂環式炭化水素類、メチルクロライド、エチルクロライド、エチレンクロライド等のハロゲン化炭化水素類等が挙げられる。無機系物理発泡剤としては、二酸化炭素、窒素、空気等の不活性ガス、水が用いられる。また上記の物理発泡剤に化学発泡剤を併用することもできる。該化学発泡剤としては、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、アゾビスイソブチロニトリル、重炭酸ナトリウム等が挙げられる。これらの中でも、積層発泡シートの二次発泡性を調整する上で、ブタン或いは、ブタンを主成分とする混合発泡剤が好ましい。 As the foaming agent that is press-fitted into the extruder, an organic physical foaming agent, an inorganic physical foaming agent, or the like can be used alone or in combination of two or more. Examples of the organic physical blowing agent include aliphatic hydrocarbons such as propane, normal butane, isobutane, isopentane, normal pentane, and hexane, alicyclic hydrocarbons such as cyclopentane and cyclohexane, methyl chloride, ethyl chloride, and ethylene. And halogenated hydrocarbons such as chloride. As the inorganic physical foaming agent, an inert gas such as carbon dioxide, nitrogen, air, or water is used. A chemical foaming agent can be used in combination with the above physical foaming agent. Examples of the chemical foaming agent include azodicarbonamide, dinitrosopentamethylenetetramine, azobisisobutyronitrile, sodium bicarbonate, and the like. Among these, in order to adjust the secondary foamability of the laminated foamed sheet, butane or a mixed foaming agent containing butane as a main component is preferable.
前記ポリスチレン系樹脂と共に押出機に供給される気泡調整剤としては、タルク、シリカ等の無機粉末や、多価カルボン酸の酸性塩、多価カルボン酸と炭酸ナトリウム或いは重炭酸ナトリウムとの反応混合物等が挙げられる。気泡調整剤の添加量は、樹脂１００重量部当たり、０．３〜２重量部程度である。 Examples of the air conditioner supplied to the extruder together with the polystyrene resin include inorganic powders such as talc and silica, acidic salts of polyvalent carboxylic acids, reaction mixtures of polyvalent carboxylic acids with sodium carbonate or sodium bicarbonate, etc. Is mentioned. The addition amount of the bubble regulator is about 0.3 to 2 parts by weight per 100 parts by weight of the resin.
そして、本発明の積層発泡シートは、特に、積層発泡シートの発泡剤残存量を通常の値よりも少なくすることと、積層発泡シートの押出方向と幅方向の加熱収縮挙動の主原因となる積層発泡シートの押出方向と幅方向の残留歪の差を調整して小さくすることにより製造される。 And the laminated foam sheet of the present invention is a laminate which is the main cause of the heat shrinkage behavior in the extrusion direction and the width direction of the laminated foam sheet, in particular, the amount of foaming agent remaining in the laminated foam sheet is less than the normal value. It is manufactured by adjusting and reducing the difference in the residual strain between the extrusion direction and the width direction of the foam sheet.
そのことを図１に基づいて説明すると、発泡剤の残存量を少なくすることにより、積層発泡シートの二次発泡厚みの変化を緩やかにすることができるので、二次発泡厚みの変化が緩やかな二次発泡厚みの水平領域が現れ、成形可能な加熱時間の範囲が広くなり、表面粗さの変化が緩やかな表面粗さの水平領域と二次発泡厚みの水平領域とを同期させることができるので、表面粗さの小さい成形体を得ることができる。また、積層発泡シートの押出方向と幅方向の残留歪を調整して差を小さくすることにより、中心線表面粗さの最大値を小さくすることができ、その結果、表面粗さの水平領域の値が極めて小さな値となる。 This will be explained with reference to FIG. 1. By reducing the remaining amount of the foaming agent, the change in the secondary foam thickness of the laminated foam sheet can be moderated, so the change in the secondary foam thickness is gentle. A horizontal region of secondary foaming thickness appears, the range of heating time that can be molded is widened, and the horizontal region of surface roughness and the horizontal region of secondary foaming thickness can be synchronized with a gradual change in surface roughness. Therefore, a molded product having a small surface roughness can be obtained. Moreover, by adjusting the residual strain in the extrusion direction and the width direction of the laminated foam sheet to reduce the difference, the maximum value of the centerline surface roughness can be reduced, and as a result, the horizontal surface roughness can be reduced. The value is extremely small.
なお、積層発泡シート中の発泡剤の残存量および積層発泡シートの押出方向と幅方向の残留歪の具体的な値としては、前述の通りである。 In addition, the specific value of the residual amount of the foaming agent in the laminated foamed sheet and the residual strain in the extrusion direction and the width direction of the laminated foamed sheet is as described above.
本発明の積層発泡シートは、従来公知の成形方法によって成形することができ、特に絞り比（成形体深さ／成形体上面開口部面積を円に換算した場合の直径）０．５以上の深絞り成形性に優れている。成形方法としては、真空成形、圧空成形や、これらの応用として、フリードローイング成形、プラグアンドリッジ成形、リッジ成形、マッチドモールド成形、ストレート成形、ドレープ成形、リバースドロー成形、エアスリップ成形、プラグアシスト成形、プラグアシストリバースロード成形等やこれらを組合せた方法等が採用される。上記成形方法の中でも、積層発泡シートの金型密着性を向上させるようなマッチドモールト゛成形等が好ましく採用される。 The laminated foam sheet of the present invention can be molded by a conventionally known molding method, and in particular, a drawing ratio (molded body depth / diameter when the molded body upper surface opening area is converted into a circle) is 0.5 or more deep. Excellent drawability. Forming methods include vacuum forming, compressed air forming, and free drawing forming, plug and ridge forming, ridge forming, matched mold forming, straight forming, drape forming, reverse draw forming, air slip forming, plug assist forming. Plug assisted reverse load molding or the like, or a combination of these methods is employed. Among the above molding methods, matched mold molding or the like that improves the mold adhesion of the laminated foamed sheet is preferably employed.
以下、本発明の積層発泡シートについて、実施例により具体的に説明する。但し、本発明は実施例に限定するものではない。 Hereinafter, the laminated foam sheet of the present invention will be specifically described with reference to examples. However, the present invention is not limited to the examples.
実施例１
ポリスチレン系樹脂として、ＰＳジャパン株式会社製Ｇ０００２を使用し、該ポリスチレン系樹脂１００重量部に対してタルク０．９０重量部を配合した原料を内径１１５ｍｍの押出機に投入して加熱溶融混練することにより溶融樹脂とし、該溶融樹脂にイソブタン６５重量％とノルマルブタン３５重量％の混合ブタン発泡剤を圧入して混練し、溶融樹脂混合物とした。なお、発泡剤の添加量は、ポリスチレン系樹脂１００重量部に対して３．３重量部である。
次いで、上記１１５ｍｍの押出機の下流側に接続された内径１８０ｍｍの押出機にて、上記発泡性溶融混合樹脂をブレーカー部の測定温度が１５６℃となるように冷却して発泡性溶融樹脂混合物とし、該発泡性溶融樹脂混合物を出口部分のテーパー角７°、出口間隙０．６７ｍｍの環状ダイを通して、押出発泡させ、その直後に内側から温度２５℃の冷却エアを風量１．８ｍ３／minで吹きつけ、同時に外側から温度２５℃の冷却エア４．５ｍ３／minを吹き付けながら、円筒状の発泡体とし、該発泡体の内面を直径６６８ｍｍの円柱状冷却装置側面上を通過させながら冷却した後、押出方向に２箇所切り開くことにより約１０４０ｍｍ巾の２枚の発泡シートを得た。マンドレルの直径をダイ出口の口径で割った値のブローアップ比は３．７とした。このとき、ダイ内のシャフト部分に１３０℃に設定したオイルを循環させ継続的に除熱を行った。
Example 1
Use G0002 manufactured by PS Japan Co., Ltd. as a polystyrene resin, and put the raw material in which 0.90 part by weight of talc is blended with 100 parts by weight of the polystyrene resin into an extruder with an inner diameter of 115 mm and heat-melt knead. Thus, a molten butane foaming agent of 65% by weight of isobutane and 35% by weight of normal butane was pressed into the molten resin and kneaded to obtain a molten resin mixture. In addition, the addition amount of a foaming agent is 3.3 weight part with respect to 100 weight part of polystyrene resins.
Next, the foamable molten mixed resin is cooled by an extruder having an inner diameter of 180 mm connected to the downstream side of the 115 mm extruder so that the measurement temperature of the breaker portion is 156 ° C. to obtain a foamable molten resin mixture. The foamable molten resin mixture is extruded and foamed through an annular die having an outlet portion taper angle of 7 ° and an outlet gap of 0.67 mm. Immediately thereafter, cooling air at a temperature of 25 ° C. is blown from the inside at an air volume of 1.8 m 3 / min. While blowing, cooling air of 4.5 m 3 / min at a temperature of 25 ° C. was blown from the outside at the same time to form a cylindrical foam, and the inner surface of the foam was cooled while passing over the side of a columnar cooling device having a diameter of 668 mm. Thereafter, two foamed sheets having a width of about 1040 mm were obtained by cutting two portions in the extrusion direction. The blow-up ratio obtained by dividing the mandrel diameter by the die exit diameter was 3.7. At this time, the oil set at 130 ° C. was circulated through the shaft portion in the die to continuously remove heat.
上記方法にて得られた発泡シートを養生した後、以下の押出ラミネート方式により該発泡シート片面に樹脂層を形成した。
他の押出機に、耐衝撃性ポリスチレンとしてＰＳジャパン株式会社製４７５Ｄを投入し、次いで溶融、混練してＴダイを通して発泡シートの外表面側（円柱状冷却装置冷却面と反対面側）に２４０℃の溶融樹脂を押出して１ｍ２当たり１２８ｇとなるように無延伸樹脂層を積層接着し、厚み２．２７ｍｍ、坪量が３７５ｇ／ｍ２の積層発泡シートを得た。
得られた積層発泡シートの発泡層見掛け密度、樹脂層坪量、積層発泡シート厚み（一次厚み）ｈ、最大二次発泡厚みＴ、樹脂層中心線表面粗さ、積層発泡シートブタン残存量、発泡層表層部の厚み方向の気泡径が５〜７０μｍの平均気泡数、１４５℃での押出方向の加熱後寸法（Ａ）と幅方向の加熱後寸法（Ｂ）等を測定した結果を表１に示す。
After curing the foamed sheet obtained by the above method, a resin layer was formed on one side of the foamed sheet by the following extrusion lamination method.
In another extruder, 475D made by PS Japan Co., Ltd. was charged as impact-resistant polystyrene, then melted and kneaded, and passed through a T-die to the outer surface side of the foamed sheet (on the opposite side to the cooling surface of the cylindrical cooling device). A non-stretched resin layer was laminated and adhered so as to be 128 g per 1 m 2 by extruding a molten resin at 0 ° C. to obtain a laminated foam sheet having a thickness of 2.27 mm and a basis weight of 375 g / m 2 .
Foam layer apparent density of the obtained laminate foam sheet, resin layer basis weight, laminate foam sheet thickness (primary thickness) h, maximum secondary foam thickness T, resin layer centerline surface roughness, laminate foam sheet butane residual amount, foam Table 1 shows the results of measurement of the average number of bubbles having a cell diameter in the thickness direction of the layer surface layer portion of 5 to 70 μm, the post-heating dimension (A) in the extrusion direction at 145 ° C., the post-heating dimension (B) in the width direction, and the like. Show.
得られた積層発泡シートを用いて、樹脂層が外側になるようにマッチドモールト゛成形法により熱成形して、口径がφ１４１ｍｍ、深さ７３ｍｍ、絞り比０．５２の丼状容器成形体を製造した。 Using the obtained laminated foam sheet, thermoformed by a matched molding method so that the resin layer is on the outer side, and manufactured a bowl-shaped container molded body having a diameter of 141 mm, a depth of 73 mm, and a drawing ratio of 0.52. .
積層発泡シート成形性、得られた成形体の印刷性を評価した結果を併せて表１に示す。
なお、成形性の判定は、ナキ、中割れ、ドローダウンによる加熱ムラのいずれも発生しなかった場合を○とし、ナキ、中割れ、ドローダウンによる加熱ムラのいずれか一つでも発生した場合を×とした。
また、容器の印刷性の判定は、熱成形した直後に曲面印刷をして、印刷ぬけ、印刷かすれが無く鮮明に印刷がなされている場合を◎とし、鮮明さにおいて多少劣るが印刷ぬけ、かすれが見られない場合を○とし、印刷ぬけ、かすれのいずれか一つでも有る場合を×とした。
The results of evaluating the laminated foam sheet formability and the printability of the obtained molded product are shown together in Table 1.
In addition, the moldability is judged as ○ when no unevenness of heating due to naki, middle crack, or drawdown occurs, and when any one of uneven heating due to cracking, intermediate cracking, or drawdown occurs. X.
In addition, the judgment of the printability of the container is ◎ when curved printing is performed immediately after thermoforming and printing is clear and there is no print fading. The case where no is seen is indicated by ◯, and the case where any one of printing and fading is observed is indicated by ×.
実施例２
ポリスチレン系樹脂１００重量部に対してタルク０．８５重量部を配合した原料を用い、発泡シート製造時の発泡剤注入量を３．２重量部とし、シートの引取速度を実施例１の約７１％に減速し、発泡層の見掛け密度を０．１５９とした以外は実施例１と同様に製造し、表１に示す発泡層厚み（ｍｍ）、発泡層見掛け密度、樹脂層坪量、積層発泡シート一次厚みｈのシートを得た。
Example 2
Using a raw material in which 0.85 parts by weight of talc is blended with 100 parts by weight of polystyrene resin, the amount of blowing agent injected at the time of foam sheet production is 3.2 parts by weight, and the sheet take-up speed is about 71 of Example 1. %, And the foam layer was manufactured in the same manner as in Example 1 except that the apparent density of the foam layer was 0.159, and the foam layer thickness (mm), foam layer apparent density, resin layer basis weight, and laminated foaming shown in Table 1 A sheet having a sheet primary thickness h was obtained.
実施例３
ポリスチレン系樹脂１００重量部に対してタルク０．８０重量部を配合した原料を用い、発泡シート製造時の発泡剤注入量を３．２重量部とし、円筒状の発泡体を外側から温度２５℃の冷却エア４．０ｍ３／minを吹き付け、Ｔダイを通して発泡シートの外表面側に２２０℃の溶融樹脂を押出した以外は実施例１と同様に製造し、表１に示す発泡層厚み（ｍｍ）、発泡層見掛け密度、樹脂層坪量、積層発泡シート一次厚みｈのシートを得た。なお、得られた積層発泡シートを熱成形して得られた容器成形体の発泡層表層部には、厚み方向の気泡径が４０μｍ程度の微細気泡が多数発生しており、該発泡層表層部の気泡径５〜７０μｍの平均気泡数は４５０個／ｍｍ２（発泡層表層部の全気泡数に対する百分率７５％）であった。
Example 3
The raw material which mix | blended 0.80 weight part of talc with respect to 100 weight part of polystyrene-type resin was used, the amount of foaming agents injection | pouring at the time of foam sheet manufacture was 3.2 weight part, and a cylindrical foam was made into temperature 25 degreeC from the outside. cooling air 4.0m blowing 3 / min, except was extruded 220 ° C. of the molten resin on the outer surface side of the foamed sheet through a T-die was produced in the same manner as in example 1, the foam layer thickness (mm shown in Table 1 ), A foam layer apparent density, a resin layer basis weight, and a laminated foam sheet primary thickness h was obtained. In addition, in the foam layer surface layer portion of the container molded body obtained by thermoforming the obtained laminated foam sheet, a large number of fine bubbles having a cell diameter in the thickness direction of about 40 μm are generated, and the foam layer surface layer portion The average number of bubbles with a bubble diameter of 5 to 70 μm was 450 / mm 2 (percentage of 75% with respect to the total number of bubbles in the surface layer portion of the foam layer).
比較例１
発泡シート製造時にダイ内のシャフト部分の除熱を行わず、発泡剤注入量を３．８重量部とし、ダイ出口間隙を０．５６ｍｍとし、ダイ出口径を変更してブロー比を４．０とした以外は実施例１と同様に製造し、表１に示す発泡層厚み（ｍｍ）、発泡層見掛け密度、樹脂層坪量、積層発泡シート一次厚みｈのシートを得た。
Comparative Example 1
No heat is removed from the shaft portion in the die during foam sheet production, the amount of blowing agent injected is 3.8 parts by weight, the die exit gap is 0.56 mm, the die exit diameter is changed, and the blow ratio is 4.0. A sheet having the foam layer thickness (mm), foam layer apparent density, resin layer basis weight, and laminated foam sheet primary thickness h shown in Table 1 was obtained in the same manner as in Example 1.
比較例２
発泡シート製造時にダイ内のシャフト部分の除熱を行わず、ダイ出口部分のテーパー角度を５°とし発泡剤注入量を３．６重量部とした以外は実施例１と同様に製造し、表１に示す発泡層厚み（ｍｍ）、発泡層見掛け密度、樹脂層坪量、積層発泡シート一次厚みｈのシートを得た。
Comparative Example 2
The heat treatment was not performed on the shaft portion in the die during the production of the foam sheet, and the production was performed in the same manner as in Example 1 except that the taper angle of the die exit portion was 5 ° and the amount of foaming agent injected was 3.6 parts by weight. A sheet having a foam layer thickness (mm), a foam layer apparent density, a resin layer basis weight, and a laminated foam sheet primary thickness h shown in FIG.
Claims (4)
Ｔ−０．２５ｈ ≦ ｔ ≦ Ｔ （１）
（但し、Ｔは該積層発泡シートの最大二次発泡厚み（ｍｍ）、ｔは最大二次発泡厚みＴ（ｍｍ）に達するまでの該積層発泡シートの二次発泡厚み（ｍｍ）である。） Thickness h consisting of a polystyrene resin foam layer having an apparent density of 0.08 to 0.20 g / cm 3 and a polystyrene resin layer having a basis weight of 50 to 180 g / m 2 provided on at least one surface of the foam layer. Is a polystyrene-based resin laminated foam sheet having a thickness of 1.5 to 3.0 mm, and when the laminated foam sheet is subjected to secondary foaming by changing the heating time under a heating temperature condition of 145 ° C., the following conditional expression ( The center line surface roughness of the surface of the polystyrene-based resin layer of the laminated foamed sheet after secondary foaming exhibiting secondary foam thickness t (mm) satisfying 1) is 0.1 to 1.2 μm. Polystyrene-based resin laminated foam sheet.
T−0.25h ≦ t ≦ T (1)
(However, T is the maximum secondary foam thickness (mm) of the laminated foam sheet, and t is the secondary foam thickness (mm) of the laminate foam sheet until the maximum secondary foam thickness T (mm) is reached.)
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| WO2014129344A1 (en) * | 2013-02-22 | 2014-08-28 | 電気化学工業株式会社 | Multilayer resin sheet for deep drawing and molded container |
| JP2015127106A (en) * | 2013-12-27 | 2015-07-09 | 積水化成品工業株式会社 | Laminated foam sheet, and resin molding |
| JP2015193192A (en) * | 2014-03-31 | 2015-11-05 | 株式会社ジェイエスピー | polystyrene resin laminated foam |
| JP2018062180A (en) * | 2018-01-10 | 2018-04-19 | 積水化成品工業株式会社 | Laminated and foamed sheet, secondary foamed sheet, container and method for producing them |
| CN115038581A (en) * | 2020-01-20 | 2022-09-09 | 日清食品控股株式会社 | Foam paper laminate, method for producing same, and foam paper container |
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| WO2014129344A1 (en) * | 2013-02-22 | 2014-08-28 | 電気化学工業株式会社 | Multilayer resin sheet for deep drawing and molded container |
| KR20150121096A (en) * | 2013-02-22 | 2015-10-28 | 덴카 주식회사 | Multilayer resin sheet for deep drawing and molded container |
| JPWO2014129344A1 (en) * | 2013-02-22 | 2017-02-02 | デンカ株式会社 | Multi-layer resin sheet for deep drawing and molded container |
| KR102244432B1 (en) | 2013-02-22 | 2021-04-23 | 덴카 주식회사 | Multilayer resin sheet for deep drawing and molded container |
| JP2015127106A (en) * | 2013-12-27 | 2015-07-09 | 積水化成品工業株式会社 | Laminated foam sheet, and resin molding |
| JP2015193192A (en) * | 2014-03-31 | 2015-11-05 | 株式会社ジェイエスピー | polystyrene resin laminated foam |
| JP2018062180A (en) * | 2018-01-10 | 2018-04-19 | 積水化成品工業株式会社 | Laminated and foamed sheet, secondary foamed sheet, container and method for producing them |
| CN115038581A (en) * | 2020-01-20 | 2022-09-09 | 日清食品控股株式会社 | Foam paper laminate, method for producing same, and foam paper container |
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