JP5193105B2 - Polystyrene-based resin laminated foam sheet and molded article - Google Patents

Polystyrene-based resin laminated foam sheet and molded article Download PDF

Info

Publication number
JP5193105B2
JP5193105B2 JP2009076249A JP2009076249A JP5193105B2 JP 5193105 B2 JP5193105 B2 JP 5193105B2 JP 2009076249 A JP2009076249 A JP 2009076249A JP 2009076249 A JP2009076249 A JP 2009076249A JP 5193105 B2 JP5193105 B2 JP 5193105B2
Authority
JP
Japan
Prior art keywords
polystyrene
foam sheet
heating
length
range
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
JP2009076249A
Other languages
Japanese (ja)
Other versions
JP2010228182A (en
Inventor
孝 今野
晃司 植田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sekisui Kasei Co Ltd
Original Assignee
Sekisui Kasei Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sekisui Kasei Co Ltd filed Critical Sekisui Kasei Co Ltd
Priority to JP2009076249A priority Critical patent/JP5193105B2/en
Publication of JP2010228182A publication Critical patent/JP2010228182A/en
Application granted granted Critical
Publication of JP5193105B2 publication Critical patent/JP5193105B2/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Description

本発明は、食品包装容器などを熱成形するのに適したポリスチレン系樹脂積層発泡シートに関し、特に、成形体の形状が深絞り形状であり多数個の成形体を一度に成型する場合であっても、各部の樹脂密度が均一であり、側壁の強度に優れた成形体を得ることができるポリスチレン系樹脂積層発泡シート及びそれを用いた成形体に関する。   The present invention relates to a polystyrene-based resin-laminated foam sheet suitable for thermoforming food packaging containers and the like, particularly when the shape of the molded body is a deep-drawn shape and a large number of molded bodies are molded at once. In addition, the present invention relates to a polystyrene-based resin laminated foam sheet capable of obtaining a molded article having a uniform resin density in each part and having excellent side wall strength, and a molded article using the same.

カップ入り即席麺などの食品包装容器に使用されているポリスチレン系樹脂発泡シートにおいて、該発泡シートの表面にポリスチレン系樹脂非発泡フィルムを積層したポリスチレン系樹脂積層発泡シートは、軽量で、断熱性が高く、高強度の割れ難い容器として広く使用されている。
一方、消費者等からの食品の低価格化の要求に応えるために、食品包装容器においても発泡シート層の軽量化やフィルム層の薄肉化の要求は常にあり、近年の容器リサイクル法の施行によりその要求は益々強くなっている。
In polystyrene resin foam sheets used for food packaging containers such as instant noodles in cups, polystyrene resin laminate foam sheets in which a polystyrene resin non-foam film is laminated on the surface of the foam sheet are lightweight and have heat insulation properties. Widely used as a high-strength, high-strength container.
On the other hand, in order to meet the demand for lower food prices from consumers, there is always a demand for lighter foam sheet layers and thinner film layers in food packaging containers. The demand is getting stronger.

この要求に対応するため、食品包装容器の軽量化が検討されてきたが、その弊害として、軽量化にしたがって特に容器の圧縮強度が弱くなることが挙げられる。これを改善するためのものとして、容器形状に熱成形した際に容器の圧縮強度を改善し得るポリスチレン系樹脂発泡シートが特許文献1に提案されている。
特許文献1には、ポリスチレン系樹脂発泡シートと、耐衝撃性ポリスチレン系樹脂シートとが積層された熱成形用ポリスチレン系樹脂多層発泡シートにおいて、該熱成形用ポリスチレン系樹脂多層発泡シートの厚みが1.5〜3.0mmであり、1m当たりの質量である坪量が340〜410g/mであり、該熱成形用ポリスチレン系樹脂多層発泡シートの引張荷重(但し、JIS K7127に準拠する。)が押出方向及び幅方向のいずれにおいても85〜150Nである熱成形用ポリスチレン系樹脂多層発泡シートが開示されている。
In order to meet this demand, weight reduction of food packaging containers has been studied, but the adverse effect is that the compressive strength of the container is particularly weakened as the weight is reduced. As a means for improving this, Patent Document 1 proposes a polystyrene-based resin foam sheet that can improve the compressive strength of a container when thermoformed into a container shape.
In Patent Document 1, in a polystyrene resin multilayer foam sheet for thermoforming in which a polystyrene resin foam sheet and an impact-resistant polystyrene resin sheet are laminated, the thickness of the polystyrene resin multilayer foam sheet for thermoforming is 1 The basis weight as a mass per 1 m 2 is 340 to 410 g / m 2 , and the tensile load of the polystyrene-based resin multilayer foamed sheet for thermoforming (however, conforming to JIS K7127). ) Is a thermoforming polystyrene-based resin multilayer foam sheet in which both the extrusion direction and the width direction are 85 to 150 N.

特開2001−293822号公報JP 2001-293822 A

しかしながら、特許文献1に開示された構成のポリスチレン系樹脂積層発泡シートは、該シートを熱成形して多数の容器を作製する際に、作製された容器の個々の強度にバラツキが生じ易いという問題があった。
ポリスチレン系樹脂積層発泡シートに熱成形を施し一度の成形サイクルで多数の容器を作製する場合には、それに対応する寸法のポリスチレン系樹脂積層発泡シートを加熱し、それぞれの容器形成領域にて該シートを容器形状に深絞り成形し、各容器を切り離して作製している。本発明者らの知見では、ここで使用するポリスチレン系樹脂積層発泡シートのシート押出方向(以下、MD方向と記す。)と幅方向(以下、TD方向と記す。)とのそれぞれの伸びのバランスが悪くなると、前記熱成形時の成形位置によって容器各個の樹脂密度が不均一となり、得られる容器の強度にバラツキを生じ易くなることが分かった。
このように、従来のポリスチレン系樹脂積層発泡シートを用いて一度に多数の容器を熱成形する(以下、多数個取りと記す。)場合、得られた容器の強度、特に、容器の上下方向に加わる力に対する強度である天地圧縮強度にバラツキが生じ、天地圧縮強度の低い容器が生じる可能性がある。
However, the polystyrene-based resin laminated foam sheet having the configuration disclosed in Patent Document 1 has a problem that when the sheet is thermoformed to produce a large number of containers, the individual strengths of the produced containers tend to vary. was there.
When a polystyrene-based resin-laminated foam sheet is thermoformed to produce a large number of containers in a single molding cycle, the polystyrene-based resin-laminated foam sheet having the corresponding dimensions is heated, and the sheet is formed in each container forming region. Is deep-drawn into a container shape, and each container is cut off. According to the knowledge of the present inventors, the balance of elongation in the sheet extrusion direction (hereinafter referred to as MD direction) and the width direction (hereinafter referred to as TD direction) of the polystyrene-based resin laminated foamed sheet used here. It was found that the resin density of each container becomes non-uniform depending on the molding position at the time of thermoforming and the strength of the resulting container tends to vary.
Thus, when a large number of containers are thermoformed at once using the conventional polystyrene-based resin laminated foam sheet (hereinafter, referred to as “multiple picking”), the strength of the obtained container, particularly in the vertical direction of the container, There is a possibility that the top and bottom compression strength, which is the strength against the applied force, varies, and a container with low top and bottom compression strength is generated.

本発明は、前記事情に鑑みてなされ、ポリスチレン系樹脂積層発泡シートのMD方向とTD方向との伸びのバランスが良く、多数個取り且つ深絞り形状の成形体の製造であっても強度バラツキの少ない成形体を製造し得るポリスチレン系樹脂積層発泡シートの提供を目的とする。   The present invention has been made in view of the above circumstances, and has a good balance of elongation between the MD direction and the TD direction of the polystyrene resin laminated foamed sheet, and even when manufacturing a large number of deep-drawn shaped molded products, there is no variation in strength. An object of the present invention is to provide a polystyrene-based resin laminated foam sheet that can produce a small number of molded articles.

前記目的を達成するため、本発明は、ポリスチレン系樹脂発泡シートの一方の面又は両面に熱可塑性樹脂非発泡フィルムが積層されてなるポリスチレン系樹脂積層発泡シートにおいて、前記ポリスチレン系樹脂積層発泡シートの厚みが1.5〜3.0mmの範囲であり、1m当たりの質量である坪量が310〜420g/mの範囲であり、JIS K7161(1994)に準拠して測定される前記ポリスチレン系樹脂発泡シートの押出方向(MD方向)及び幅方向(TD方向)の、前記ポリスチレン系樹脂積層発泡シートの引張強度が50〜75Nの範囲であり、 In order to achieve the above object, the present invention provides a polystyrene resin laminated foam sheet in which a thermoplastic resin non-foamed film is laminated on one or both surfaces of a polystyrene resin foam sheet. thickness in the range of 1.5 to 3.0 mm, in the range basis weight is the mass per 1 m 2 of 310~420g / m 2, the polystyrene which is measured according to JIS K7161 (1994) extrusion direction of the resin foam sheet (MD direction) and width direction (TD direction), the tensile strength of the polystyrene resin laminate foam sheet Ri range der of 50~75N,

前記押出方向と前記幅方向の所定間隔の加熱前長さを測定した前記ポリスチレン系樹脂積層発泡シートを125℃に設定したオーブン内に150秒間静置し、前記押出方向と幅方向の所定間隔の加熱後長さを測定した場合に、
前記押出方向の加熱前長さ(MD1)に対する加熱後長さ(MD2)の比である押出方向加熱変形(MD2/MD1)が0.95〜1.15の範囲であり、
前記幅方向の加熱前長さ(TD1)に対する加熱後長さ(TD2)の比である幅方向加熱変形(TD2/TD1)が0.95〜1.15の範囲であり、且つ
前記押出方向の加熱前長さ(MD1)と前記幅方向の加熱前長さ(TD1)とを同じとした場合の前記押出方向の加熱後長さ(MD2)と前記幅方向の加熱後長さ(TD2)との比である加熱後の長さの比(TD2/MD2)が0.90〜1.10の範囲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を提供する。
The polystyrene-based resin laminated foamed sheet, whose length before heating at a predetermined interval in the extrusion direction and the width direction was measured, was left in an oven set at 125 ° C. for 150 seconds, and the predetermined interval in the extrusion direction and the width direction was When measuring the length after heating,
The extrusion direction heating deformation (MD2 / MD1), which is the ratio of the post-heating length (MD2) to the pre-heating length (MD1) in the extrusion direction , is in the range of 0.95 to 1.15,
The widthwise heating deformation (TD2 / TD1), which is the ratio of the length after heating (TD2) to the length before heating (TD1) in the width direction , is in the range of 0.95 to 1.15, and
The heating after the length of the extrusion direction (MD2) and post-heating length in the width direction in the case where said heating before the length of the extrusion direction (MD1) and heated before the length of the width direction (TD1) and the same A ratio of length after heating (TD2 / MD2), which is a ratio to (TD2), is in the range of 0.90 to 1.10 .

また本発明は、前記ポリスチレン系樹脂積層発泡シートを熱成形して得られた成形体を提供する。   Moreover, this invention provides the molded object obtained by thermoforming the said polystyrene-type resin laminated foam sheet.

本発明のポリスチレン系樹脂積層発泡シートは、厚みが1.5〜3.0mmの範囲、坪量が310〜420g/mの範囲のシートでの、JIS K7161(1994)に準拠して測定される押出方向及び幅方向の引張強度を50〜75Nの範囲としたものなので、ポリスチレン系樹脂積層発泡シートのMD方向とTD方向との伸びのバランスが良く、多数個取り且つ深絞り形状の成形体の製造であっても強度バラツキの少ない成形体を製造することができる。
本発明の成形体は、前記ポリスチレン系樹脂積層発泡シートを熱成形して得られたものであるので、深絞り形状の成形体を多数個取りで製造したものであっても強度バラツキが少なくなり、また樹脂密度も均一になることから外観のバラツキも少なくなる。
The polystyrene-based resin laminated foam sheet of the present invention is measured according to JIS K7161 (1994) in a sheet having a thickness in the range of 1.5 to 3.0 mm and a basis weight in the range of 310 to 420 g / m 2. Since the tensile strength in the extrusion direction and the width direction is in the range of 50 to 75 N, the polystyrene resin laminated foam sheet has a good balance of elongation in the MD direction and the TD direction, and is a multi-piece and deep-drawn shaped molded body Even if it is manufacture of this, a molded object with few intensity variations can be manufactured.
Since the molded product of the present invention is obtained by thermoforming the polystyrene-based resin laminated foamed sheet, even if a deep-drawn molded product is produced by taking a large number of pieces, there is less variation in strength. In addition, since the resin density is uniform, there is less variation in appearance.

実施例での試験に用いたサンプル形状を示す平面図である。It is a top view which shows the sample shape used for the test in an Example. 実施例での引張試験のMD方向のサンプリング状態を示す平面図である。It is a top view which shows the sampling state of MD direction of the tension test in an Example. 実施例での引張試験のTD方向のサンプリング状態を示す平面図である。It is a top view which shows the sampling state of the TD direction of the tension test in an Example. 実施例での加熱変形試験のサンプリング状態を示す平面図である。It is a top view which shows the sampling state of the heat deformation test in an Example.

本発明のポリスチレン系樹脂積層発泡シートは、ポリスチレン系樹脂発泡シートの一方の面又は両面に熱可塑性樹脂非発泡フィルムが積層されてなり、厚みが1.5〜3.0mmの範囲であり、1m当たりの質量である坪量が310〜420g/mの範囲であり、JIS K7161(1994)に準拠して測定されるMD方向及びTD方向の引張強度が50〜75Nの範囲であることを特徴としている。 The polystyrene resin laminated foam sheet of the present invention is formed by laminating a thermoplastic resin non-foamed film on one surface or both surfaces of a polystyrene resin foam sheet, and has a thickness in the range of 1.5 to 3.0 mm. The basis weight which is the mass per 2 is in the range of 310 to 420 g / m 2 , and the tensile strength in the MD direction and TD direction measured in accordance with JIS K7161 (1994) is in the range of 50 to 75N. It is a feature.

前記ポリスチレン系樹脂発泡シートを構成するポリスチレン系樹脂としては、スチレン単独重合体又はスチレンを主成分とするスチレンと他のモノマーとの共重合体(スチレン系共重合体)、又はこれらの混合物、或いは前記スチレン単独重合体及びスチレン系共重合体の群から選択される1種又は2種以上を主成分とし、これに他の樹脂やゴムを副成分として混合した混合樹脂等が挙げられる。前記スチレン系共重合体としては、スチレン−無水マレイン酸共重合体、スチレン−アクリロニトリル共重合体、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−ブタジエン共重合体、スチレン−ブタジエン−アクリロニトリル共重合体等が挙げられる。また前記副成分として混合される樹脂やゴムとしては、ブタジエンゴム、ブタジエン−スチレン共重合体ゴム等が挙げられる。   As the polystyrene resin constituting the polystyrene resin foam sheet, a styrene homopolymer, a copolymer of styrene mainly composed of styrene and another monomer (styrene copolymer), or a mixture thereof, or Examples thereof include mixed resins in which one or two or more selected from the group of styrene homopolymers and styrene copolymers are used as a main component, and other resins and rubbers are mixed as subcomponents. Examples of the styrene copolymer include styrene-maleic anhydride copolymer, styrene-acrylonitrile copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-butadiene copolymer, styrene- Examples thereof include a butadiene-acrylonitrile copolymer. Examples of the resin and rubber mixed as the accessory component include butadiene rubber and butadiene-styrene copolymer rubber.

前記ポリスチレン系樹脂には、必要に応じて無機充填材、気泡調整剤、滑剤、難燃剤、難燃助剤、酸化防止剤、紫外線吸収剤、顔料、着色剤などのポリスチレン系樹脂発泡体の製造分野において周知の各種添加物を添加してもよい。   Production of polystyrene resin foams such as inorganic fillers, air conditioners, lubricants, flame retardants, flame retardant aids, antioxidants, UV absorbers, pigments, colorants, etc. as necessary for the polystyrene resins. Various additives well known in the art may be added.

前記ポリスチレン系樹脂発泡シートは、前記ポリスチレン系樹脂と、必要に応じて添加される前記添加物とを、先端にサーキュラーダイ等のシート製造用ダイを取り付けた押出機内に投入し、押出機内部で材料を加熱溶融し、混合しながら発泡剤を圧入、混合し、その発泡剤混入樹脂を適当な温度に冷却後、押出機先端のダイのスリットから押出し、押出直後にエアーを吹き付けて冷却しながら発泡シートを製造する従来公知の製造方法によって製造可能である。   The polystyrene-based resin foam sheet is charged with the polystyrene-based resin and the additive that is added as necessary into an extruder having a sheet die such as a circular die attached to the tip. The material is heated and melted, and the foaming agent is injected and mixed while mixing. After cooling the foaming agent-containing resin to an appropriate temperature, the resin is extruded from the slit of the die at the tip of the extruder, and air is blown immediately after the extrusion while cooling It can be produced by a conventionally known production method for producing a foam sheet.

ポリスチレン系樹脂発泡シートの製造に用いる発泡剤としては、プロパン、n−ブタン、i−ブタン、n−ブタンとi−ブタンとの混合物、ペンタン、ヘキサン等の脂肪族炭化水素、シクロブタン、シクロペンタン等の環式脂肪族炭化水素、トリクロロフロロメタン、ジクロロジフロロメタン、1,1−ジフルオロエタン、1,1−ジフルオロ−1−クロロエタン、1,1,1,2−テトラフルオロエタン、メチルクロライド、エチルクロライド、メチレンクロライド等のハロゲン化炭化水素およびこれらの混合物等の物理発泡剤を使用することができ、それらの中でもn−ブタン、i−ブタン、n−ブタンとi−ブタンとの混合物、ペンタン等の脂肪族炭化水素が好ましい。これらの発泡剤は単独でもよいし、二種類以上を混合して用いてもよい。
さらに、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の分解型発泡剤を使用したり、二酸化炭素等の無機ガスや水を使用することもできる。更に、上記各種の発泡剤を適宜混合して用いることもできる。
Examples of the foaming agent used in the production of the polystyrene resin foam sheet include propane, n-butane, i-butane, a mixture of n-butane and i-butane, aliphatic hydrocarbons such as pentane and hexane, cyclobutane, and cyclopentane. Cycloaliphatic hydrocarbons, trichlorofluoromethane, dichlorodifluoromethane, 1,1-difluoroethane, 1,1-difluoro-1-chloroethane, 1,1,1,2-tetrafluoroethane, methyl chloride, ethyl chloride Physical foaming agents such as halogenated hydrocarbons such as methylene chloride and mixtures thereof, among which n-butane, i-butane, a mixture of n-butane and i-butane, pentane, etc. Aliphatic hydrocarbons are preferred. These blowing agents may be used alone or in combination of two or more.
Furthermore, as a foaming agent, use a decomposable foaming agent such as azodicarbonamide, dinitrosopentamethylenetetramine, azobisisobutyronitrile, sodium bicarbonate, or use an inorganic gas such as carbon dioxide or water. You can also. Furthermore, the above-mentioned various foaming agents can be appropriately mixed and used.

本発明において、使用するポリスチレン系樹脂発泡シートの厚さは1.50〜2.80mmの範囲が好ましく、1.85〜2.50mmの範囲がより好ましい。
また、ポリスチレン系樹脂発泡シートの坪量(シート坪量)は、120〜320g/mの範囲が好ましく、150〜300g/mの範囲がより好ましい。
また、ポリスチレン系樹脂発泡シートの密度は、0.06〜0.25g/cmの範囲が好ましく、0.08〜0.16g/cmの範囲がより好ましい。この範囲の密度を有するポリスチレン系樹脂発泡シートは、発泡倍数が4〜17倍の範囲であり、好ましくは6〜13倍の範囲となる。
In the present invention, the thickness of the polystyrene-based resin foam sheet used is preferably 1.50 to 2.80 mm, and more preferably 1.85 to 2.50 mm.
The basis weight of polystyrene-based resin foam sheet (sheet basis weight) is preferably in the range of 120~320g / m 2, the range of 150 to 300 g / m 2 is more preferable.
The density of the polystyrene-based resin foam sheet is preferably in the range of 0.06 to 0.25 g / cm 3 , and more preferably in the range of 0.08 to 0.16 g / cm 3 . The polystyrene resin foam sheet having a density in this range has a foam expansion ratio in the range of 4 to 17 times, and preferably in the range of 6 to 13 times.

本発明のポリスチレン系樹脂積層発泡シートに用いられる前記熱可塑性樹脂非発泡フィルムとしては、スチレン、メチルスチレン、エチルスチレン、イソプロピルスチレン、ジメチルスチレン、パラメチルスチレン、クロロスチレン、ブロモスチレン、ビニルトルエン、ビニルキシレンの単独重合体又は共重合体、例えば樹脂としてはスチレン−無水マレイン酸共重合体、スチレン・アクリル酸共重合体、ハイインパクトポリスチレン(耐衝撃性ポリスチレン)、スチレン・アクリロニトリル樹脂、アクリロニトリル・ブタジエン−スチレン樹脂が使用できる。特に、ポリスチレン樹脂及びハイインパクトポリスチレン樹脂が好ましい。その他に、ポリスチレン系樹脂とハイインパクトポリスチレンとの混合又は耐衝撃性ポリスチレン単独であってかつ、ハイインパクトポリスチレンにはスチレン−ブタジエン共重合体がサラミ構造状に分散し、その粒径が0.3μm〜10μmのものを多く含むものをあげることができる。またその他に、線状低密度ポリエチレン、高密度ポリエチレン、低密度ポリエチレン、プロピレンホモポリマー、エチレン・プロピレンランダムポリマー、エチレン・プロピレンブロックポリマー、エチレン・プロピレン−ブテン−ターポリマー、エチレン−酢酸ビニル共重合体、エチレン−不飽和カルボン酸エステル共重合体(例えば、エチレン−メチルメタクリレート共重合体)、エチレン−不飽和カルボン酸金属塩共重合体(例えば、エチレン−アクリル酸マグネシウム(又は亜鉛)共重合体)、プロピレン−塩化ビニルコポリマー、プロピレン−ブテンコポリマー、プロピレン−無水マレイン酸コポリマー、プロピレン−オレフィン共重合体(プロピレン−エチレン共重合体、プロピレン−ブテン−1共重合体)ポリエチレン又はポリプロピレンの不飽和カルボン酸(例えば、無水マレイン酸)変性物、エチレン−プロピレンゴム、アタクチックポリプロピレン等が挙げられ、ポレエチレン、エチレン−プロピレン共重合体、プロピレン−ブテン−1共重合体及びこれら2種以上の混合物やポリエチレンテレフタレート、ポリブチレンテレフタレート等のフィルムが挙げられる。   Examples of the thermoplastic resin non-foamed film used in the polystyrene resin laminated foam sheet of the present invention include styrene, methylstyrene, ethylstyrene, isopropylstyrene, dimethylstyrene, paramethylstyrene, chlorostyrene, bromostyrene, vinyltoluene, vinyl Xylene homopolymers or copolymers, such as styrene-maleic anhydride copolymer, styrene / acrylic acid copolymer, high impact polystyrene (impact polystyrene), styrene / acrylonitrile resin, acrylonitrile / butadiene- Styrene resin can be used. In particular, polystyrene resin and high impact polystyrene resin are preferable. In addition, it is a mixture of polystyrene resin and high impact polystyrene or high impact polystyrene alone, and styrene-butadiene copolymer is dispersed in a salami structure in high impact polystyrene, and its particle size is 0.3 μm. The thing containing many things of 10 micrometers can be mention | raise | lifted. In addition, linear low density polyethylene, high density polyethylene, low density polyethylene, propylene homopolymer, ethylene / propylene random polymer, ethylene / propylene block polymer, ethylene / propylene / butene / terpolymer, ethylene / vinyl acetate copolymer , Ethylene-unsaturated carboxylic acid ester copolymer (for example, ethylene-methyl methacrylate copolymer), ethylene-unsaturated carboxylic acid metal salt copolymer (for example, ethylene-magnesium acrylate (or zinc) copolymer) , Propylene-vinyl chloride copolymer, propylene-butene copolymer, propylene-maleic anhydride copolymer, propylene-olefin copolymer (propylene-ethylene copolymer, propylene-butene-1 copolymer) polyethylene or polyethylene Propylene-modified unsaturated carboxylic acid (for example, maleic anhydride), ethylene-propylene rubber, atactic polypropylene, and the like. Polyethylene, ethylene-propylene copolymer, propylene-butene-1 copolymer, and these two types Examples thereof include films such as the above mixtures, polyethylene terephthalate, polybutylene terephthalate and the like.

さらにガスバリヤ性を持つフィルムを積層することも好ましい態様であり、ガスバリヤ性フィルムとしては、エチレン・酢酸ビニル系共重合体、ポリビニルアルコール、ポリ塩化ビニリデン、ポリアミド、ポリエステル、ポリアクリロニトリル、塩化ビニリデン系・アクリロニトリル共重合体、アクリロニトリル系メチルメタアクリレート・ブタジエン共重合体、ナイロン、二軸延伸ナイロン、二軸延伸ポリエチレンテレフタレート、二軸延伸ポリプロピレン、高密度ポリエチレン、アイオノマー樹脂(例えば、登録商標サーリン)、あるいは、金属蒸着フィルムの単独、もしくは、これらフィルムの積層されたものが用いられる。   Further, it is also a preferred embodiment to laminate a film having gas barrier properties. Examples of the gas barrier film include ethylene / vinyl acetate copolymers, polyvinyl alcohol, polyvinylidene chloride, polyamide, polyester, polyacrylonitrile, vinylidene chloride / acrylonitrile. Copolymer, acrylonitrile-based methyl methacrylate / butadiene copolymer, nylon, biaxially stretched nylon, biaxially stretched polyethylene terephthalate, biaxially stretched polypropylene, high density polyethylene, ionomer resin (eg, Surlyn), or metal A vapor deposition film alone or a laminate of these films is used.

前記熱可塑性樹脂非発泡フィルムの厚さは、0.07〜0.25mmの範囲が好ましく、0.09〜0.22mmの範囲がより好ましい。
また、熱可塑性樹脂非発泡フィルムの坪量(フィルム坪量)は、75〜260g/mの範囲が好ましく、100〜230g/mの範囲がより好ましい。
前記熱可塑性樹脂非発泡フィルムは、ポリスチレン系樹脂発泡シートの一方の面に積層してもよいし、両方の面に積層してもよい。
The thickness of the thermoplastic resin non-foamed film is preferably in the range of 0.07 to 0.25 mm, and more preferably in the range of 0.09 to 0.22 mm.
The basis weight of the thermoplastic resin non-foamed film (Film basis weight) is preferably in the range of 75~260g / m 2, the range of 100~230g / m 2 is more preferable.
The thermoplastic resin non-foamed film may be laminated on one surface of the polystyrene resin foam sheet, or may be laminated on both surfaces.

前記熱可塑性樹脂非発泡フィルムをポリスチレン系樹脂発泡シートに積層する方法は、特に限定されず、例えば、
(1)熱可塑性樹脂非発泡フィルムの材料樹脂を押出機内で加熱溶融し、適当な押出温度に調温後、Tダイのスリットからフィルム上に押出し、そのままポリスチレン系樹脂発泡シート上に重ねてロール圧着して積層する方法、
(2)熱可塑性樹脂非発泡フィルムとポリスチレン系樹脂発泡シートとを共押出しする方法、
(3)予め熱可塑性樹脂非発泡フィルムとポリスチレン系樹脂発泡シートとを接着剤を用いて貼り合わせる方法、
などが挙げられる。前記接着剤としては、エチレン−酢酸ビニル共重合体、メタアクリル酸メチル重合体エラストマー(タフプレン、タフテック:旭化成工業株式会社)等のような接着剤が好ましく、その厚さは5μm〜150μm程度で使用される。
The method of laminating the thermoplastic resin non-foamed film on the polystyrene resin foam sheet is not particularly limited, for example,
(1) Thermoplastic resin The non-foamed film material resin is heated and melted in an extruder, adjusted to an appropriate extrusion temperature, extruded onto the film from the slit of the T-die, and rolled on the polystyrene resin foam sheet as it is. Pressure bonding and laminating,
(2) A method of co-extruding a thermoplastic resin non-foamed film and a polystyrene resin foam sheet,
(3) A method of pasting together a thermoplastic resin non-foamed film and a polystyrene resin foam sheet using an adhesive,
Etc. As the adhesive, an adhesive such as an ethylene-vinyl acetate copolymer, a methyl methacrylate polymer elastomer (Tufprene, Tuftec: Asahi Kasei Kogyo Co., Ltd.) or the like is preferable, and the thickness is about 5 μm to 150 μm. Is done.

本発明のポリスチレン系樹脂積層発泡シートは、厚みが1.5〜3.0mmの範囲、好ましくは1.7〜2.8mmの範囲であり、坪量が310〜420g/mの範囲、好ましくは320〜410g/mの範囲である。
厚みが1.5mm未満であると、熱成形した容器の強度が低くなり、3.0mmを超えると熱成形した容器の形状が熱成形型の形状を再現しにくくなる。
また、坪量が310g/m未満であると、熱成形した容器の強度不足や成形不良が発生しやすくなり、420g/mを超えると熱成形した容器の重量が重くなる。
The polystyrene resin laminated foam sheet of the present invention has a thickness in the range of 1.5 to 3.0 mm, preferably in the range of 1.7 to 2.8 mm, and the basis weight in the range of 310 to 420 g / m 2 , preferably Is in the range of 320-410 g / m 2 .
When the thickness is less than 1.5 mm, the strength of the thermoformed container is lowered, and when it exceeds 3.0 mm, the shape of the thermoformed container is difficult to reproduce the shape of the thermoforming mold.
Further, if the basis weight is less than 310 g / m 2 , insufficient strength and poor molding of the thermoformed container are likely to occur, and if it exceeds 420 g / m 2 , the thermoformed container becomes heavy.

本発明のポリスチレン系樹脂積層発泡シートは、JIS K7161(1994)に準拠して測定されるMD方向及びTD方向の引張強度が50〜75Nの範囲であり、55〜73Nの範囲がより好ましい。
この引張強度が50N未満であると、そのポリスチレン系樹脂積層発泡シートを用いて深絞り加工により容器を作製する際に、成形不良となり易く、また強度や外観に優れた容器を製造することが難しくなる。引張強度が75Nを超えると、ポリスチレン系樹脂積層発泡シートのMD方向とTD方向との伸びのバランスが悪くなり、多数個取り且つ深絞り形状の容器を製造する場合に、得られる容器の強度、特に、容器の天地圧縮強度にバラツキが生じ易くなる。
本発明のポリスチレン系樹脂積層発泡シートにおいて、MD方向及びTD方向の引張強度を50〜75Nの範囲に調整するための方法としては、例えば、次の方法が挙げられる。
(a)ポリスチレン系樹脂発泡シートの製造時、押出直後に吹き付けるエアーの温度と量を適宜調整する方法、
(b)発泡シートを製造する金型の口径を変え、ブローアップ比(プラグ口径/金型口径)を調製する方法、等がある。
The polystyrene-based resin laminated foam sheet of the present invention has a tensile strength in the MD direction and TD direction measured in accordance with JIS K7161 (1994) in the range of 50 to 75N, and more preferably in the range of 55 to 73N.
When the tensile strength is less than 50N, when a container is produced by deep drawing using the polystyrene-based resin laminated foam sheet, it is difficult to form a container and it is difficult to produce a container excellent in strength and appearance. Become. When the tensile strength exceeds 75 N, the balance of the elongation in the MD direction and the TD direction of the polystyrene-based resin laminated foam sheet is deteriorated, and the strength of the container obtained when producing a multi-piece and deep-drawn container, In particular, variations in the vertical compression strength of the container are likely to occur.
Examples of the method for adjusting the tensile strength in the MD direction and the TD direction in the range of 50 to 75 N in the polystyrene-based resin laminated foam sheet of the present invention include the following methods.
(A) A method of appropriately adjusting the temperature and amount of air blown immediately after extrusion during the production of a polystyrene resin foam sheet,
(B) There is a method of adjusting the blow-up ratio (plug diameter / die diameter) by changing the diameter of the mold for producing the foam sheet.

本発明の好適な実施形態において、ポリスチレン系樹脂積層発泡シートは、MD方向とTD方向の所定間隔の加熱前長さを測定したポリスチレン系樹脂積層発泡シートを125℃中に150秒間静置し、前記MD方向とTD方向の所定間隔の加熱後長さを測定した場合に、
(1)MD方向の加熱前長さ(MD1)に対する加熱後長さ(MD2)の比であるMD方向加熱変形(MD2/MD1)が0.95〜1.15の範囲であり、
(2)TD方向の加熱前長さ(TD1)に対する加熱後長さ(TD2)の比であるTD方向加熱変形(TD2/TD1)が0.95〜1.15の範囲であり、且つ
(3)MD方向の加熱前長さ(MD1)とTD方向の加熱前長さ(TD1)とを同じとした場合のMD方向の加熱後長さ(MD2)とTD方向の加熱後長さ(TD2)との比である加熱後の長さの比(TD2/MD2)が0.90〜1.10の範囲であることが好ましい。
前記(1)〜(3)の条件を全て満たしていれば、加熱時のポリスチレン系樹脂積層発泡シートのMD方向とTD方向との伸びのバランスが良くなり、多数個取り且つ深絞り形状の容器を製造する場合であっても、得られる容器の天地圧縮強度にバラツキが生じ難くなる。
ポリスチレン系樹脂積層発泡シートの加熱変形特性を前記範囲に入るように調整するには、ポリスチレン系樹脂発泡シートの製造時、押出直後に吹き付けるエアーの温度と量を適宜調整する方法、発泡シートを製造する金型の口径を変え、ブローアップ比(プラグ口径/金型口径)を調製する方法、等がある。
In a preferred embodiment of the present invention, the polystyrene-based resin laminated foam sheet is a polystyrene-based resin laminated foam sheet whose length before heating measured at a predetermined interval in the MD direction and the TD direction is allowed to stand at 125 ° C. for 150 seconds, When measuring the length after heating at a predetermined interval in the MD direction and the TD direction,
(1) MD direction heating deformation (MD2 / MD1), which is a ratio of the length after heating (MD2) to the length before heating in the MD direction (MD1) (MD2 / MD1), is in the range of 0.95 to 1.15,
(2) The TD direction heating deformation (TD2 / TD1), which is the ratio of the length after heating (TD2) to the length before heating (TD1) in the TD direction, is in the range of 0.95 to 1.15, and (3 ) Length after heating in the MD direction (MD2) and length after heating in the TD direction (TD2) when the length before heating in the MD direction (MD1) and the length before heating in the TD direction (TD1) are the same. It is preferable that the ratio (TD2 / MD2) of the length after heating which is a ratio of 0.90 to 1.10.
If all of the above conditions (1) to (3) are satisfied, the balance of the elongation in the MD direction and the TD direction of the polystyrene-based resin laminated foam sheet during heating is improved, and a multi-piece and deep-drawn container Even in the case of manufacturing, variation in the vertical compression strength of the resulting container is less likely to occur.
To adjust the heat deformation characteristics of a polystyrene resin laminated foam sheet to fall within the above range, a method for appropriately adjusting the temperature and amount of air blown immediately after extrusion during the production of a polystyrene resin foam sheet, a foam sheet is produced. For example, there is a method for adjusting the blow-up ratio (plug diameter / die diameter) by changing the diameter of the mold.

本発明のポリスチレン系樹脂積層発泡シートは、従来より周知の熱成形法によって、様々な形状や寸法の容器、例えば、カップ入り即席麺などのカップや丼、弁当容器、トレーなどの食品包装容器を製造するための材料として好適である。   The polystyrene-based resin laminated foam sheet of the present invention can be applied to containers of various shapes and dimensions, for example, cups and bowls such as instant noodles in cups, bowls, lunch containers, trays and other food packaging containers by a conventionally known thermoforming method. It is suitable as a material for manufacturing.

本発明のポリスチレン系樹脂積層発泡シートを用い、熱成形法により深絞り加工して、カップ形状の容器を製造する場合、得られる容器の天地圧縮強度は、100〜200Nの範囲が好ましく、120〜180Nの範囲がより好ましい。また、天地圧縮強度の最大値と最小値との差が40N以下であることが好ましく、35N以下であることがより好ましい。   When producing a cup-shaped container by deep drawing by the thermoforming method using the polystyrene-based resin laminated foam sheet of the present invention, the top and bottom compressive strength of the resulting container is preferably in the range of 100 to 200 N, 120 to A range of 180 N is more preferable. Further, the difference between the maximum value and the minimum value of the top and bottom compression strength is preferably 40 N or less, and more preferably 35 N or less.

以下、本発明を実施例により更に具体的に説明するが、以下の実施例の記載は例示に過ぎず、本発明は以下の実施例の記載にのみ限定されるものではない。
まず、以下の実施例1〜3及び比較例1〜4で製造したポリスチレン系樹脂積層発泡シートについて行った測定の方法を記す。
EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, description of the following Examples is only an illustration and this invention is not limited only to description of the following Examples.
First, the method of the measurement performed about the polystyrene-type resin laminated foam sheet manufactured in the following Examples 1-3 and Comparative Examples 1-4 is described.

<シート厚みの測定方法>
発泡シートの幅方向の両端20mmを除いた部分を、幅方向50mm間隔の位置を測定点とする。この測定点をダイヤルシックネスゲージSM−112(テクロック社製)を使用し、厚みを最小単位0.01mmまで測定する。この測定値の平均値を、発泡シートのシート厚み〔mm〕とする。
<Measuring method of sheet thickness>
The position excluding both ends 20 mm in the width direction of the foam sheet is taken as the measurement point at the positions in the width direction at 50 mm intervals. The measurement point is measured using a dial thickness gauge SM-112 (manufactured by Teclock Corporation), and the thickness is measured to the minimum unit of 0.01 mm. Let the average value of this measured value be sheet thickness [mm] of a foam sheet.

<シート坪量の測定方法>
発泡シートの幅方向の両端20mmを除いた部分を、幅方向に等間隔に10cm×10cmに切り取り、各切片の質量〔g〕を0.001g単位まで測定する。各切片の質量〔g〕の平均値を1m当たりの質量に換算した値を、発泡シートのシート坪量〔g/m〕とする。
<Measuring method of sheet basis weight>
A portion excluding both ends 20 mm in the width direction of the foam sheet is cut into 10 cm × 10 cm at equal intervals in the width direction, and the mass [g] of each section is measured to 0.001 g unit. A value obtained by converting an average value of the mass [g] of each section into a mass per 1 m 2 is defined as a sheet basis weight [g / m 2 ] of the foam sheet.

<発泡倍数>
使用したポリスチレン系樹脂の密度(1.05〔g/cm〕とする)にシート厚み〔mm〕を乗じ、さらにシート坪量〔g/m〕で除し、さらに10を乗じた値を、発泡シートの発泡倍数〔倍〕とする。
<Foaming multiple>
A value obtained by multiplying the density (1.05 [g / cm 3 ]) of the used polystyrene resin by the sheet thickness [mm], further dividing by the sheet basis weight [g / m 2 ], and further multiplying by 10 3 Is the expansion factor [times] of the foam sheet.

<フィルム坪量の測定方法>
使用した熱可塑性樹脂非発泡フィルムの密度(1.05〔g/cm〕とする)にフィルム厚み〔mm〕を乗じ、さらに10を乗じた値をフィルム坪量〔g/m〕とする。
<Measurement method of film basis weight>
The film basis weight [g / m 2 ] is obtained by multiplying the density (1.05 [g / cm 3 ]) of the used thermoplastic resin non-foamed film by the film thickness [mm] and further multiplying by 10 3. To do.

<積層坪量の測定方法>
積層発泡シートの幅方向の両端20mmを除いた部分を、幅方向に等間隔に10cm×10cmに切り取り、各切片の質量〔g〕を0.001g単位まで測定する。各切片の質量〔g〕の平均値を1m当たりの質量に換算した値を、積層発泡シートの積層坪量〔g/m〕とする。
<Measurement method of lamination basis weight>
A portion excluding both ends 20 mm in the width direction of the laminated foam sheet is cut into 10 cm × 10 cm at equal intervals in the width direction, and the mass [g] of each section is measured to 0.001 g unit. The value obtained by converting the average value of the mass [g] of each section into the mass per 1 m 2 is defined as the lamination basis weight [g / m 2 ] of the laminated foamed sheet.

<引張強度の測定方法>
引張強度の測定方法についてはJIS K−7161(1994)に準拠した方法で測定した。
試験片については、MD方向、TD方向ともに、JIS K7127記載のタイプ5の型を用いてシート両端50mmを除いた等間隔の5箇所より切り抜く。
図1は、本実施例での引張強度の測定に用いたサンプル1の形状を示す。このサンプルは幅広の両側部と細長い中央部とを有する形状をなしており、各部寸法はa=115mm、b=25mm、c=6mmとした。
図2は、本実施例での引張試験のMD方向のサンプリング状態を示す平面図である。各部寸法はd=50mm、eは等間隔を示す。製造したポリスチレン系樹脂積層発泡シート3のMD方向に沿って、シート両端50mmを除いた等間隔の5箇所よりサンプル1を切り取った。
図3は、本実施例での引張試験のTD方向のサンプリング状態を示す平面図である。各部寸法はd=50mm、eは等間隔を示す。製造したポリスチレン系樹脂積層発泡シート3のMD方向に沿って、シート両端50mmを除いた等間隔の5箇所よりサンプル1を切り取った。
テンシロン万能試験機 UCT−10T(オリエンテック社製)を用い、つかみ間距離を80mmに設定し、引張速度500mm/minで測定した。この時の最大引張荷重の平均値を引張強度(単位:N)とした。
<Measurement method of tensile strength>
About the measuring method of tensile strength, it measured by the method based on JISK-7161 (1994).
About a test piece, it cuts out from five places of equal intervals except the sheet | seat both ends 50mm using the type | mold type | mold of JISK7127 for MD direction and TD direction.
FIG. 1 shows the shape of sample 1 used for measurement of tensile strength in this example. This sample has a shape having a wide side part and an elongated central part, and the dimensions of each part are a = 115 mm, b = 25 mm, and c = 6 mm.
FIG. 2 is a plan view showing a sampling state in the MD direction of the tensile test in this example. The dimensions of each part are d = 50 mm, and e is an equal interval. Samples 1 were cut out from five equally spaced locations excluding 50 mm at both ends of the sheet along the MD direction of the produced polystyrene-based resin laminated foamed sheet 3.
FIG. 3 is a plan view showing a sampling state in the TD direction of the tensile test in this example. The dimensions of each part are d = 50 mm, and e is an equal interval. Samples 1 were cut out from five equally spaced locations excluding 50 mm at both ends of the sheet along the MD direction of the produced polystyrene-based resin laminated foamed sheet 3.
Using a Tensilon universal testing machine UCT-10T (Orientec Co., Ltd.), the distance between grips was set to 80 mm, and the tensile speed was 500 mm / min. The average value of the maximum tensile load at this time was taken as the tensile strength (unit: N).

<加熱変形の測定方法>
加熱変形については、得られたポリスチレン系樹脂積層発泡シートの両端50mmを除いて均等間隔で5箇所を10mm角の切片に切り取る。
図4は、加熱変形の試験サンプリング状態を示す平面図である。各部寸法はd=50mm、eは等間隔を表す、f=100mm、g=100mmである。
TD方向とMD方向にあらかじめそれぞれ100mmの線分を引き、その長さを加熱前のTD方向長さ、MD方向長さとした。
そして加熱オーブン(ヤマト科学社製、ファインオーブンDH−41)を用い、あらかじめ125℃に設定したオーブン内にすばやく試験片を入れ、150秒後にすばやく取り出し、あらかじめひかれた線分の長さを表裏で測定し、その平均を加熱後のTD方向長さ、MD方向長さとした。
TD比、MD比、加熱後の長さの比(TD/MD)は以下の式で求める。
TD比=加熱後のTD方向長さ[mm]/加熱前のTD方向長さ[mm]
MD比=加熱後のMD方向長さ[mm]/加熱前のMD方向長さ[mm]
TD/MD=加熱後のTD方向長さ[mm]/加熱後のMD方向長さ[mm]
また、前記TD比、MD比の最大値と最小値との差を算出した(R)。
<Measurement method of heat deformation>
About heat deformation, 5 parts are cut out to a 10 mm square piece at equal intervals except for 50 mm at both ends of the obtained polystyrene-based resin laminated foam sheet.
FIG. 4 is a plan view showing a test sampling state of heat deformation. The dimensions of each part are d = 50 mm, e is an equal interval, f = 100 mm, and g = 100 mm.
A line segment of 100 mm was drawn in advance in each of the TD direction and the MD direction, and the length was defined as the TD direction length before heating and the MD direction length.
And using a heating oven (manufactured by Yamato Scientific Co., Ltd., Fine Oven DH-41), quickly put the test piece in the oven set at 125 ° C. in advance, take it out quickly after 150 seconds, and measure the length of the line segment drawn in advance. The average was taken as the TD direction length and MD direction length after heating.
The TD ratio, MD ratio, and ratio of length after heating (TD / MD) are determined by the following formula.
TD ratio = TD direction length after heating [mm] / TD direction length before heating [mm]
MD ratio = MD direction length after heating [mm] / MD direction length before heating [mm]
TD / MD = TD direction length after heating [mm] / MD direction length after heating [mm]
Further, the difference between the maximum value and the minimum value of the TD ratio and MD ratio was calculated (R).

<天地圧縮強度の測定法法>
テンシロン万能試験機RTG−1310(オリエンテック社製)を用い、表面に空気抜き用の溝が掘られた専用板の上に容器を底部が上になるように設置する。φ120mmの圧縮板で、試験速度100mm/minで容器を圧縮する。最大30mmまで圧縮し、この時の最大荷重の平均値をその容器の天地圧縮強度(単位:N)とする。
また、その容器の天地圧縮強度の最大値と最小値との差を算出した(R)。
<Method for measuring top and bottom compression strength>
Using a Tensilon universal testing machine RTG-1310 (manufactured by Orientec Co., Ltd.), a container is placed on a dedicated plate with a groove for air venting on the surface so that the bottom is on the top. The container is compressed at a test speed of 100 mm / min with a compression plate of φ120 mm. It compresses to a maximum of 30 mm, and let the average value of the maximum load at this time be the vertical compression strength (unit: N) of the container.
Moreover, the difference between the maximum value and the minimum value of the vertical compression strength of the container was calculated (R).

[実施例1]
ポリスチレン樹脂(製品名:G0002(A&M社製、MI=2.1)を100質量%に発泡剤としてブタンガス(イソブタン/ノルマルブタン=50/50)、3.3質量部、気泡調整剤として粉末タルク0.85部相当のマスターバッチ品(電化スチロール社製DSM−1401A)を使用して、これを最高温度260℃に設定された押出機に投入し、押出機内で溶融混練させ、その後樹脂温度153℃に冷却調整して、押出機先端に取り付けた口径170mmのサーキュラーダイのスリット(クリアランス0.45mm)より円筒状に押出した。
押出直後に32℃のエアーを内側で0.05m/m、外側で0.13m/mの割合で吹き付けて、厚み2.1mm、シート坪量240g/m、発泡倍数9.2倍のポリスチレン系樹脂発泡シートを得た。得られた環状発泡シートは2枚のシートに切り裂いてロール状のポリスチレン発泡シートを得た。
発泡ガスの置換の為、14日間保管したポリスチレン系樹脂発泡シートを用い、積層シートを作製した。ハイインパクトポリスチレン樹脂(東洋スチレン社製、製品名:E−641N)を最高温度240℃に設定した120φ押出機で溶融し、Tダイよりフィルム状に押出し、冷却しきらないうちにフィルム坪量130g/mになるように調整して前記ポリスチレン系樹脂発泡シートの表面に重ねて積層し、積層発泡シートを得、これを巻き取る直前にシリコン成分が一定になるようにシリコン塗布装置(ニッカ社製)を使用して吹き付け、積層坪量370g/mの最終的なポリスチレン系樹脂積層発泡シートを得た。
得られたポリスチレン系樹脂積層発泡シートの引張強度はTD方向=71.6N、MD方向=67.1Nであった。加熱変形についてはTD方向0.97、MD方向1.00であった。よって加熱後の長さ比はTD/MD=0.97であった。
得られた積層発泡シートを内径130mmφ、深さ70mmの容器を1回の成形で縦6個、横6個(合計36個)得られる成形装置にフィルム面が外側になるように供給して容器の成形を行った。
得られた容器について、天地圧縮強度を測定を行った。その結果、平均は143N、最大−最小値の差R=31.3Nであった。
[Example 1]
Polystyrene resin (product name: G0002 (manufactured by A & M, MI = 2.1) to 100% by mass, butane gas as isolating agent (isobutane / normal butane = 50/50), 3.3 parts by mass, powder talc as air conditioner Using a master batch product equivalent to 0.85 parts (DSM-1401A manufactured by Denki Styrol Co., Ltd.), this was put into an extruder set at a maximum temperature of 260 ° C., melted and kneaded in the extruder, and then the resin temperature 153 It was cooled to 0 ° C. and extruded into a cylindrical shape from a slit (clearance 0.45 mm) of a circular die having a diameter of 170 mm attached to the tip of the extruder.
0.05 m 3 / m 2 the air 32 ° C. inside immediately after extrusion, by blowing at a rate of 0.13 m 3 / m 2 on the outside, thickness 2.1 mm, sheet basis weight 240 g / m 2, expansion ratio 9. A double polystyrene resin foam sheet was obtained. The obtained annular foam sheet was cut into two sheets to obtain a roll-shaped polystyrene foam sheet.
A laminated sheet was prepared using a polystyrene resin foam sheet stored for 14 days for replacement of the foam gas. High impact polystyrene resin (product name: E-641N, manufactured by Toyo Styrene Co., Ltd.) is melted with a 120φ extruder set at a maximum temperature of 240 ° C., extruded into a film from a T-die, and the film has a basis weight of 130 g before being cooled. / m was adjusted to 2 by laminating superimposed on the polystyrene resin foam surface of the sheet to obtain a laminated foam sheet, which silicon coating apparatus so that the silicon component becomes constant immediately before winding the (Nikka Co. And a final polystyrene-based resin laminated foamed sheet having a laminated basis weight of 370 g / m 2 was obtained.
The tensile strength of the obtained polystyrene-based resin laminated foam sheet was TD direction = 71.6N and MD direction = 67.1N. The heat deformation was 0.97 in the TD direction and 1.00 in the MD direction. Therefore, the length ratio after heating was TD / MD = 0.97.
The obtained laminated foamed sheet is supplied to a molding apparatus in which a container having an inner diameter of 130 mmφ and a depth of 70 mm is formed in a single molding and obtained 6 in length and 6 in width (36 in total) with the film surface facing outward. Was molded.
About the obtained container, the top and bottom compression strength was measured. As a result, the average was 143N, and the difference between the maximum and minimum values was R = 31.3N.

[実施例2]
ポリスチレン系樹脂発泡シートに積層するハイインパクトポリスチレン樹脂のフィルム坪量を160g/mに変更し、最終的なポリスチレン系樹脂積層発泡シートの積層坪量を400g/mとしたこと以外は、実施例1と同様にして、ポリスチレン系樹脂積層発泡シート及び容器を作製した。
測定結果をまとめて表1に記す。
[Example 2]
Except that the film basis weight of the high-impact polystyrene resin laminated on the polystyrene resin foam sheet was changed to 160 g / m 2 and the final basis weight of the polystyrene resin laminate foam sheet was changed to 400 g / m 2 In the same manner as in Example 1, a polystyrene resin laminated foam sheet and a container were produced.
The measurement results are summarized in Table 1.

[実施例3]
ポリスチレン系樹脂発泡シート作製時に発泡剤としてブタンガス(イソブタン/ノルマルブタン=50/50)、3.5質量部に変更し、厚み2.1mm、シート坪量220g/m、発泡倍数10.0倍のポリスチレン系樹脂発泡シートを得たこと、さらにポリスチレン系樹脂発泡シートに積層するハイインパクトポリスチレン樹脂のフィルム坪量を100g/mに変更し、最終的なポリスチレン系樹脂積層発泡シートの積層坪量を310g/mとしたこと以外は、実施例1と同様にして、ポリスチレン系樹脂積層発泡シート及び容器を作製した。
測定結果をまとめて表1に記す。
[Example 3]
Butane gas (isobutane / normal butane = 50/50) as a foaming agent at the time of preparing a polystyrene resin foam sheet, changed to 3.5 parts by mass, thickness 2.1 mm, sheet basis weight 220 g / m 2 , foaming factor 10.0 times The polystyrene basis resin foam sheet was obtained, and the film basis weight of the high impact polystyrene resin laminated on the polystyrene resin foam sheet was changed to 100 g / m 2 , and the final basis weight of the polystyrene resin laminate foam sheet was changed. A polystyrene resin laminated foam sheet and a container were produced in the same manner as in Example 1 except that the amount was 310 g / m 2 .
The measurement results are summarized in Table 1.

[比較例1]
ポリスチレン系樹脂発泡シート作製の押出直後に27℃のエアーを内側で0.10m/m、外側で0.16m/mで吹き付けて、厚み2.1mm、坪量240g/m、発泡倍数9.2倍のポリスチレン系樹脂発泡シートを得たこと以外は、実施例1と同様にして、ポリスチレン系樹脂積層発泡シート及び容器を作製した。
得られたポリスチレン系樹脂積層発泡シートは、引張強度がTD方向で82.3N、MD方向で77.8Nであり、本発明の引っ張り強度の範囲外であった。
測定結果をまとめて表1に記す。
[Comparative Example 1]
0.10 m 3 / m 2 the air immediately after the 27 ° C. extruded polystyrene resin foam sheet produced inside, by spraying the outside at 0.16 m 3 / m 2, thickness 2.1 mm, basis weight 240 g / m 2, A polystyrene resin laminated foam sheet and a container were produced in the same manner as in Example 1 except that a polystyrene resin foam sheet having a foaming ratio of 9.2 times was obtained.
The obtained polystyrene-based resin laminated foam sheet had a tensile strength of 82.3N in the TD direction and 77.8N in the MD direction, and was outside the range of the tensile strength of the present invention.
The measurement results are summarized in Table 1.

[比較例2]
ポリスチレン系樹脂発泡シート作製の押出直後に27℃のエアーを内側で0.12m/m、外側で0.16m/mで吹き付けて、厚み2.1mm、坪量240g/m、発泡倍数9.2倍のポリスチレン系樹脂発泡シートを得たこと以外は、実施例2と同様にして、ポリスチレン系樹脂積層発泡シート及び容器を作製した。
得られたポリスチレン系樹脂積層発泡シートは、引張強度がTD方向で89.2N、MD方向で82.3Nであり、本発明の引っ張り強度の範囲外であった。
測定結果をまとめて表1に記す。
[Comparative Example 2]
0.12 m 3 / m 2 the air immediately after the 27 ° C. extruded polystyrene resin foam sheet produced inside, by spraying the outside at 0.16 m 3 / m 2, thickness 2.1 mm, basis weight 240 g / m 2, A polystyrene resin laminated foam sheet and a container were produced in the same manner as in Example 2 except that a polystyrene resin foam sheet having a foaming ratio of 9.2 times was obtained.
The obtained polystyrene-based resin laminated foam sheet had a tensile strength of 89.2N in the TD direction and 82.3N in the MD direction, and was outside the range of the tensile strength of the present invention.
The measurement results are summarized in Table 1.

[比較例3]
ポリスチレン系樹脂発泡シート作製時の金型口径を155mmのものに変更したこと、押出直後に27℃のエアーを内側で0.12m/m、外側で0.16m/mで吹き付けて、厚み2.1mm、坪量240g/m、発泡倍数9.2倍のポリスチレン系樹脂発泡シートを得たこと以外は、実施例1と同様にして、ポリスチレン系樹脂積層発泡シート及び容器を作製した。
得られたポリスチレン系樹脂積層発泡シートは、引張強度がTD方向で88.5N、MD方向で83.3Nであり、本発明の引っ張り強度の範囲外であった。
測定結果をまとめて表1に記す。
[Comparative Example 3]
That the mold diameter polystyrene-based resin foam sheet when prepared was changed to the 155mm, 0.12m 3 / m 2 the air 27 ° C. inside immediately after extrusion, by blowing outside at 0.16 m 3 / m 2 A polystyrene resin laminated foam sheet and a container were produced in the same manner as in Example 1 except that a polystyrene resin foam sheet having a thickness of 2.1 mm, a basis weight of 240 g / m 2 , and an expansion ratio of 9.2 times was obtained. did.
The obtained polystyrene-based resin laminated foam sheet had a tensile strength of 88.5 N in the TD direction and 83.3 N in the MD direction, and was outside the range of the tensile strength of the present invention.
The measurement results are summarized in Table 1.

[比較例4]
ポリスチレン系樹脂発泡シート作製に用いた発泡剤をブタンガス(イソブタン/ノルマルブタン=50/50)、3.95質量部とし、厚み1.4mm、シート坪量120g/m、発泡倍数12.0倍のポリスチレン系樹脂発泡シートを作製したこと、このポリスチレン系樹脂発泡シートにハイインパクトポリスチレン樹脂をフィルム坪量100g/m、となるように積層し、積層坪量が220g/mのポリスチレン系樹脂積層発泡シートを得たこと以外は、実施例1と同様にして、ポリスチレン系樹脂積層発泡シートを作製した。
得られたポリスチレン系樹脂積層発泡シートは、引張強度がTD方向で46.5N、MD方向で46.5Nであり、本発明の引っ張り強度の範囲外であった。
測定結果をまとめて表1に記す。
前記ポリスチレン系樹脂積層発泡シートを用い、実施例1と同様の条件で容器を成形しようとしたが、熱成形時にポリスチレン系樹脂積層発泡シートが裂けたために、容器を得ることはできなかった。
[Comparative Example 4]
The foaming agent used for producing the polystyrene-based resin foam sheet is butane gas (isobutane / normal butane = 50/50), 3.95 parts by mass, the thickness is 1.4 mm, the sheet basis weight is 120 g / m 2 , and the expansion ratio is 12.0 times. A polystyrene-based resin foam sheet, a high-impact polystyrene resin was laminated on the polystyrene-based resin foam sheet so as to have a film basis weight of 100 g / m 2 , and a laminate basis weight of 220 g / m 2 polystyrene resin A polystyrene-based resin laminated foam sheet was produced in the same manner as in Example 1 except that a laminated foam sheet was obtained.
The obtained polystyrene resin laminated foam sheet had a tensile strength of 46.5 N in the TD direction and 46.5 N in the MD direction, and was outside the range of the tensile strength of the present invention.
The measurement results are summarized in Table 1.
An attempt was made to mold the container under the same conditions as in Example 1 using the polystyrene resin laminated foam sheet, but the container could not be obtained because the polystyrene resin laminated foam sheet was torn during thermoforming.

Figure 0005193105
Figure 0005193105

表1の結果から、実施例1〜3で作製したポリスチレン系樹脂積層発泡シートは、MD方向及びTD方向の引張強度が50〜75Nの範囲であり、これらのポリスチレン系樹脂積層発泡シートは、加熱変形がMD方向、TD方向共に0.95〜1.15の範囲に入っており、加熱変形しにくいものであることがわかる。
また、これらのシートは、加熱後の長さの比(TD/MD)が0.90〜1.10の範囲に入っており、加熱変形のバランスにも優れていた。
そしてこれらのシートを用い、多数取りによって容器を成形した場合、得られた容器の天地圧縮強度が120〜200Nの範囲であり、且つ天地圧縮強度の最大値と最小値との差(R)が40N以下と強度バラツキが小さくなることが分かった。
From the results in Table 1, the polystyrene resin laminated foam sheets produced in Examples 1 to 3 have a tensile strength in the MD direction and TD direction of 50 to 75 N, and these polystyrene resin laminated foam sheets are heated. It can be seen that the deformation is in the range of 0.95 to 1.15 in both the MD direction and the TD direction, and is hardly deformed by heating.
Further, these sheets had a length ratio after heating (TD / MD) in the range of 0.90 to 1.10, and were excellent in the balance of heat deformation.
And when these containers are used and a container is formed by multi-cavity, the top and bottom compression strength of the obtained container is in the range of 120 to 200 N, and the difference (R) between the maximum value and the minimum value of the top and bottom compression strength is It was found that the intensity variation was less than 40N.

一方、比較例1〜3で作製したポリスチレン系樹脂積層発泡シートは、MD方向及びTD方向の引張強度がいずれも75Nを超えており、本発明の引っ張り強度の範囲外であり、これらのポリスチレン系樹脂積層発泡シートは、加熱変形がMD方向、TD方向とも0.90〜1.10の範囲に入っているものの、(TD/MD)の値が何れも1.10を超えており、加熱変形のバランスが悪かった。
そしてこれらのシートを用い、多数取りによって容器を成形した場合、得られた容器の天地圧縮強度が120〜200Nの範囲であったが、天地圧縮強度の最大値と最小値との差(R)が42.1〜51.9Nと大きく、容器の強度バラツキが大きくなった。
On the other hand, the polystyrene-based resin laminated foam sheets prepared in Comparative Examples 1 to 3 both have a tensile strength in the MD direction and the TD direction exceeding 75 N, which is outside the range of the tensile strength of the present invention. The resin-laminated foam sheet is in the range of 0.90 to 1.10 in both the MD and TD directions, but both (TD / MD) values exceed 1.10. The balance was bad.
And when these containers were used and the container was molded by multi-cavity, the top and bottom compression strength of the obtained container was in the range of 120 to 200 N, but the difference (R) between the maximum value and the minimum value of the top and bottom compression strength. Was as large as 42.1 to 51.9 N, and the strength variation of the container became large.

また、比較例4で作製したポリスチレン系樹脂積層発泡シートは、MD方向及びTD方向の引張強度が50N未満であり、本発明の引っ張り強度の範囲外であり、このポリスチレン系樹脂積層発泡シートは、加熱変形がMD方向、TD方向とも0.90〜1.10の範囲に入っているものの、(TD/MD)の値が1.10を超えており、加熱変形のバランスが悪かった。
この比較例4のシートは、熱成形時にポリスチレン系樹脂積層発泡シートが裂けたために、容器を得ることはできなかった。
Further, the polystyrene-based resin laminated foam sheet produced in Comparative Example 4 has a tensile strength in the MD direction and TD direction of less than 50 N, which is outside the range of the tensile strength of the present invention. Although the heat deformation was in the range of 0.90 to 1.10 in both the MD direction and the TD direction, the value of (TD / MD) exceeded 1.10, and the balance of the heat deformation was poor.
The sheet of Comparative Example 4 was unable to obtain a container because the polystyrene-based resin laminated foam sheet was torn during thermoforming.

本発明のポリスチレン系樹脂積層発泡シートは、カップ入り即席麺の容器、食品包装用トレー、納豆容器などの食品包装容器の製造に好適である。   The polystyrene-based resin laminated foam sheet of the present invention is suitable for the production of food packaging containers such as cups of instant noodle containers, food packaging trays, and natto containers.

1…引張試験サンプル、2…加熱変形試験サンプル、3…ポリスチレン系樹脂積層発泡シート。   DESCRIPTION OF SYMBOLS 1 ... Tensile test sample, 2 ... Heat deformation test sample, 3 ... Polystyrene-type resin laminated foam sheet.

Claims (2)

ポリスチレン系樹脂発泡シートの一方の面又は両面に熱可塑性樹脂非発泡フィルムが積層されてなるポリスチレン系樹脂積層発泡シートにおいて、前記ポリスチレン系樹脂積層発泡シートの厚みが1.5〜3.0mmの範囲であり、1m当たりの質量である坪量が310〜420g/mの範囲であり、JIS K7161(1994)に準拠して測定される前記ポリスチレン系樹脂発泡シートの押出方向(MD方向)及び幅方向(TD方向)の、前記ポリスチレン系樹脂積層発泡シートの引張強度が50〜75Nの範囲であり、
前記押出方向と前記幅方向の所定間隔の加熱前長さを測定した前記ポリスチレン系樹脂積層発泡シートを125℃に設定したオーブン内に150秒間静置し、前記押出方向と幅方向の所定間隔の加熱後長さを測定した場合に、
前記押出方向の加熱前長さ(MD1)に対する加熱後長さ(MD2)の比である押出方向加熱変形(MD2/MD1)が0.95〜1.15の範囲であり、
前記幅方向の加熱前長さ(TD1)に対する加熱後長さ(TD2)の比である幅方向加熱変形(TD2/TD1)が0.95〜1.15の範囲であり、且つ
前記押出方向の加熱前長さ(MD1)と前記幅方向の加熱前長さ(TD1)とを同じとした場合の前記押出方向の加熱後長さ(MD2)と前記幅方向の加熱後長さ(TD2)との比である加熱後の長さの比(TD2/MD2)が0.90〜1.10の範囲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。
In a polystyrene resin laminated foam sheet in which a thermoplastic resin non-foamed film is laminated on one or both surfaces of a polystyrene resin foam sheet, the thickness of the polystyrene resin laminate foam sheet is in the range of 1.5 to 3.0 mm. , and the ranges mass basis weight of 310~420g / m 2 which is per 1 m 2, JIS K7161 wherein the polystyrene-based resin foam sheet extrusion direction as measured according to (1994) (MD direction) and width direction (TD direction), the tensile strength of the polystyrene resin laminate foam sheet Ri range der of 50~75N,
The standing extrusion direction and the 150 seconds width direction of the polystyrene-based resin laminate foam sheet was measured before heating length of predetermined intervals in an oven set to 125 ° C., the predetermined distance between the extrusion direction and the width direction When measuring the length after heating,
The extrusion direction heating deformation (MD2 / MD1), which is the ratio of the post-heating length (MD2) to the pre-heating length (MD1) in the extrusion direction, is in the range of 0.95 to 1.15,
The widthwise heating deformation (TD2 / TD1), which is the ratio of the length after heating (TD2) to the length before heating (TD1) in the width direction, is in the range of 0.95 to 1.15, and
The heating after the length of the extrusion direction (MD2) and post-heating length in the width direction in the case where said heating before the length of the extrusion direction (MD1) and heated before the length of the width direction (TD1) and the same (TD2), characterized and to Lupo polystyrene-based resin laminate foam sheet that the ratio of the length after heating is the ratio (TD2 / MD2) is in the range of 0.90 to 1.10 in.
請求項1に記載のポリスチレン系樹脂積層発泡シートを熱成形して得られた成形体。 The molded object obtained by thermoforming the polystyrene-type resin laminated foam sheet of Claim 1 .
JP2009076249A 2009-03-26 2009-03-26 Polystyrene-based resin laminated foam sheet and molded article Active JP5193105B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2009076249A JP5193105B2 (en) 2009-03-26 2009-03-26 Polystyrene-based resin laminated foam sheet and molded article

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2009076249A JP5193105B2 (en) 2009-03-26 2009-03-26 Polystyrene-based resin laminated foam sheet and molded article

Publications (2)

Publication Number Publication Date
JP2010228182A JP2010228182A (en) 2010-10-14
JP5193105B2 true JP5193105B2 (en) 2013-05-08

Family

ID=43044520

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2009076249A Active JP5193105B2 (en) 2009-03-26 2009-03-26 Polystyrene-based resin laminated foam sheet and molded article

Country Status (1)

Country Link
JP (1) JP5193105B2 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015189039A (en) * 2014-03-27 2015-11-02 積水化成品工業株式会社 Polystyrene resin laminated expanded sheet, molding and expanded container
WO2018181616A1 (en) 2017-03-29 2018-10-04 大日本印刷株式会社 Container and method for manufacturing container
JP6943737B2 (en) * 2017-11-21 2021-10-06 古河電気工業株式会社 Exterior body for electric wires and wire harness with exterior body

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59179633A (en) * 1983-03-31 1984-10-12 Sekisui Plastics Co Ltd Polystyrene sheet foam for forming deep-drawn container
JPH09123322A (en) * 1995-11-07 1997-05-13 Asahi Chem Ind Co Ltd Styrene laminated sheet and its molding
JPH09156006A (en) * 1995-12-04 1997-06-17 Kanegafuchi Chem Ind Co Ltd Styrene resin laminate foamed sheet and styrene resin foam container
JP3448759B2 (en) * 1997-03-24 2003-09-22 積水化成品工業株式会社 Thermoplastic resin laminated foam sheet and container thereof
JP3448757B2 (en) * 1997-08-12 2003-09-22 積水化成品工業株式会社 Laminated polystyrene resin foam container
JP3912701B2 (en) * 1997-10-13 2007-05-09 株式会社ジェイエスピー Polystyrene resin laminated foam sheet
JPH11236024A (en) * 1998-02-24 1999-08-31 Sekisui Plastics Co Ltd Multilayered container
JP4526051B2 (en) * 2000-04-12 2010-08-18 株式会社ジェイエスピー Polystyrene resin multilayer foam sheet for thermoforming
JP4216481B2 (en) * 2001-01-19 2009-01-28 積水化成品工業株式会社 Styrene resin foam laminate and cup noodle container using the same
JP2005088200A (en) * 2003-09-11 2005-04-07 Kaneka Corp Styrenic resin laminated foamed sheet and molded container comprising the same
JP4480455B2 (en) * 2004-05-11 2010-06-16 積水化成品工業株式会社 Polystyrene-based resin laminated foam sheet that excels in deep drawing
JP4258769B2 (en) * 2004-06-08 2009-04-30 株式会社ジェイエスピー Polystyrene resin laminated foam sheet
JP4709533B2 (en) * 2004-11-09 2011-06-22 積水化成品工業株式会社 Polystyrene-based resin laminated foam sheet that excels in deep drawing
JP4761936B2 (en) * 2005-11-05 2011-08-31 積水化成品工業株式会社 Polystyrene-based resin laminated foam sheet with excellent deep drawability
JP4938392B2 (en) * 2006-09-14 2012-05-23 積水化成品工業株式会社 Polystyrene resin laminated foam sheet and method for producing the same

Also Published As

Publication number Publication date
JP2010228182A (en) 2010-10-14

Similar Documents

Publication Publication Date Title
RU2133671C1 (en) Foamed polystyrene sheet, method for thermal forming of deep drawn products from foamed thermoplast and deep drawn product manufactured from foamed thermoplastic sheet
JP4446385B2 (en) Multi-layer polylactic acid resin foam for thermoforming
JPH0523589B2 (en)
JP5649175B2 (en) Inner fitting container using a container made of polystyrene resin laminated foam sheet as the container body
JP5427708B2 (en) Food containers using heat-resistant polystyrene resin foam laminate sheets
JP5193105B2 (en) Polystyrene-based resin laminated foam sheet and molded article
JP3732418B2 (en) Expandable styrene resin particles
US20060022366A1 (en) Method of producing polystyrene-based resin foam street
JP5932568B2 (en) Polystyrene resin laminated foam sheet
JP4484184B2 (en) Polystyrene resin foam sheet, thermoplastic resin laminated foam sheet, and containers thereof
JP4258769B2 (en) Polystyrene resin laminated foam sheet
JP5161409B2 (en) Polypropylene resin extruded foam sheet and thermoformed product of the extruded foam sheet
JP4526051B2 (en) Polystyrene resin multilayer foam sheet for thermoforming
JP4301467B2 (en) Polystyrene resin multilayer foam and container comprising the multilayer foam
JP5478320B2 (en) Polystyrene resin foam sheet
JP4338114B2 (en) Polystyrene resin foam / polyolefin resin multilayer
JP2007112456A (en) Polypropylene resin foamed container
JP2012006356A (en) Thermoplastic resin laminate foamed sheet and container
JPH11129369A (en) Synthetic resin foam sheet and its manufacture
JP4547972B2 (en) Polypropylene resin laminated foam sheet and molded body
JP3912701B2 (en) Polystyrene resin laminated foam sheet
JP2006248187A (en) Polypropylene resin-laminated foamed sheet, its manufacturing method and its molding
JP2001150610A (en) Polystyrenic resin multilayered foamed sheet for thermoforming
JP2005307024A (en) Polypropylene resin foamed sheet and molded product
TW201309459A (en) Method of manufacturing container

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20111011

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20120831

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20121002

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20121203

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A821

Effective date: 20121204

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20130115

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20130201

R150 Certificate of patent or registration of utility model

Ref document number: 5193105

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R150

Free format text: JAPANESE INTERMEDIATE CODE: R150

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20160208

Year of fee payment: 3