JP2010229375A - Foamable polystyrene base resin particle and method for manufacturing the same, preparatorily foamed particle and foamed product - Google Patents

Foamable polystyrene base resin particle and method for manufacturing the same, preparatorily foamed particle and foamed product Download PDF

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JP2010229375A
JP2010229375A JP2009081617A JP2009081617A JP2010229375A JP 2010229375 A JP2010229375 A JP 2010229375A JP 2009081617 A JP2009081617 A JP 2009081617A JP 2009081617 A JP2009081617 A JP 2009081617A JP 2010229375 A JP2010229375 A JP 2010229375A
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polystyrene resin
resin particles
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expandable polystyrene
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JP5599154B2 (en
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Yukio Aramomi
幸雄 新籾
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Sekisui Kasei Co Ltd
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Sekisui Plastics Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a foamable polystyrene base resin particle which can be preparatorily foamed to have a small foaming dispersion, can be prolonged in storage term, and can provide a good foamed product even if it is stored for a long time. <P>SOLUTION: The foamable polystyrene base resin particle comprises a polystyrene base resin particle and a foaming agent, wherein the polystyrene base resin particle can be provided by way of at least one step of melting and blending a polystyrene base resin cooled down to the glass transition point or lower and at least one step of cooling the melted and blended polystyrene base resin down to the glass transition point or lower; and the foamable polystyrene base resin particle has an adhesive moisture content of 0.05-0.45 mass%. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

本発明は、食品容器や梱包、緩衝材として有用な発泡性ポリスチレン系樹脂粒子に関し、さらに詳しくは発泡性ポリスチレン樹脂粒子の保管時間の経過による気泡変化が少なく、外観が美麗、且つ高い強度を有する成形体を得ることのできる発泡性ポリスチレン系樹脂粒子に関する。   The present invention relates to expandable polystyrene resin particles useful as food containers, packaging, and cushioning materials, and more specifically, there is little change in bubbles due to the passage of storage time of expandable polystyrene resin particles, the appearance is beautiful, and the strength is high. The present invention relates to an expandable polystyrene resin particle from which a molded product can be obtained.

食品用容器や梱包、緩衝材に用いられる発泡プラスチックとしては、優れた断熱性、経済性、衛生性をもつポリスチレン系樹脂発泡成形体が多く使用されている。一般に、工業的に行われているポリスチレン系樹脂発泡成形体の製造方法は、揮発性発泡剤等を含有した、発泡性ポリスチレン系樹脂粒子をスチーム等の熱媒体により加熱し、所望の嵩密度まで発泡(予備発泡)させた後、得られた予備発泡粒子を成形金型に充填し、再度加熱することによって発泡成形体とする型内発泡成形法が行なわれている。このとき、得られるポリスチレン系樹脂発泡成形体の密度は、ほぼ予備発泡粒子の嵩密度と同じとなる。嵩密度の設定は、発泡スチレン系成形体に要求される強度と、発泡性ポリスチレン系樹脂粒子が有する発泡性能によって決定される。例えば、家電品等の梱包材や魚箱等の食品容器に用いられるものは、およそ0.014〜0.025g/cmの密度のものが市場に供されており、特に0.017〜0.020g/cmの密度のものが多用されている。 As foamed plastics used for food containers, packaging, and cushioning materials, many polystyrene-based resin foam molded articles having excellent heat insulation, economy, and hygiene are used. Generally, a method for producing a polystyrene-based resin foam molded body that is industrially used is to heat foamable polystyrene-based resin particles containing a volatile foaming agent or the like with a heat medium such as steam to a desired bulk density. After foaming (pre-foaming), the pre-foamed particles obtained are filled into a molding die and heated again to form an in-mold foam molding method for forming a foam molded body. At this time, the density of the obtained polystyrene-based resin foam molding is substantially the same as the bulk density of the pre-expanded particles. The setting of the bulk density is determined by the strength required for the foamed styrene-based molded product and the foaming performance of the expandable polystyrene-based resin particles. For example, the thing used for food containers, such as packing materials, such as household appliances, and a fish box, is a thing with a density of about 0.014-0.025 g / cm < 3 >, and is marketed especially 0.017-0. Those with a density of .020 g / cm 3 are frequently used.

この型内発泡成形工程において、スチーム等の加熱媒体温度(水蒸気の場合は加熱蒸気圧力)によって、得られる成形体の外観、強度が変化する。例えば、水蒸気にて加熱する場合、加熱蒸気圧力を高くすると発泡成形体の外観、強度は向上する傾向にあるが、気泡の直径(気泡径)が小さく、気泡膜の厚みが薄い場合は熱に溶けることで発泡成形体の外観、強度が低下する。このように発泡成形体の気泡径は、成形性、物性面で重要な因子の一つである。   In this in-mold foam molding process, the appearance and strength of the resulting molded body change depending on the temperature of the heating medium such as steam (heated steam pressure in the case of steam). For example, when heating with steam, increasing the heating steam pressure tends to improve the appearance and strength of the foamed molded product. However, if the bubble diameter (bubble diameter) is small and the bubble film is thin, By melting, the appearance and strength of the foamed molded product are lowered. As described above, the cell diameter of the foam molded article is one of the important factors in terms of moldability and physical properties.

従来、ベース樹脂となるポリスチレン系樹脂は、単量体からの重合工程から得られたものが使用され、魚介類、野菜などの運搬、保冷などに使用される輸送箱やテレビ、冷蔵庫、洗濯機、エアコン等の家電製品の緩衝材として使用される。   Conventionally, polystyrene resins used as base resins are those obtained from the polymerization process from monomers, and are used for transporting fish, seafood, vegetables, etc., for transporting cold storage, TVs, refrigerators, washing machines. Used as a cushioning material for home appliances such as air conditioners.

しかし、従来はこれらの発泡成形体は、使用後にそのまま廃棄されていた。廃棄された製品は、埋め立てに使用されるか、又は焼却されるが、これらの処分方法は環境を害し、人にも悪影響を及ぼす為に好ましくない。
そこで、現在では使用済みの発泡成形体のリサイクル化が進み、環境保護が行われるようになってきた。
また、家電製品を構成する材料はこれを再利用することが義務付けられた。
その結果、家電製品を廃棄するに際しては、その構成材料を金属、ガラス、プラスチック等に分けて、それぞれを再利用しなければならなくなった。家電製品以外にも複写機、ファクシミリ、プリンターなどの事務用機器も金属、ガラス、プラスチックが用いられているので、これらも再利用することが望ましいとされている。
However, conventionally, these foamed molded products have been discarded as they are after use. The discarded products are used for land reclamation or incinerated, but these disposal methods are not preferable because they harm the environment and adversely affect people.
Therefore, the recycling of used foamed moldings has progressed, and environmental protection has come to be performed.
In addition, it was obliged to reuse the materials that make up home appliances.
As a result, when disposing of home appliances, it has become necessary to divide the constituent materials into metals, glass, plastics, etc., and reuse them. In addition to home appliances, office machines such as copiers, facsimiles, and printers use metal, glass, and plastic, and it is desirable to reuse them.

プラスチック材料のうち、ポリスチレン系樹脂については再利用の方法として、これを発泡性粒子とすることが提案されされている。すなわち、ポリスチレン系樹脂に発泡剤を含ませて発泡性粒子として再利用する試みが提案されている(例えば、特許文献1,2参照。)。   Among the plastic materials, it has been proposed to use polystyrene resins as expandable particles as a recycling method. That is, an attempt to reuse a polystyrene resin by adding a foaming agent as foamable particles has been proposed (for example, see Patent Documents 1 and 2).

特許文献1,2には、廃品から回収された熱可塑性樹脂、特にポリスチレン系樹脂と、発泡剤とタルク等を押出機内で溶融混練し、これを押出機の先に取付けた口金の孔から加圧液中に押し出すと同時に切断し冷却し、発泡を抑えて発泡性粒子とする方法(水中ホットカット法)が記載されている。
また、ポリスチレン系樹脂発泡成形体の特性を強化するために無機物を含有させることが検討され、その1手段としてポリスチレン系樹脂と、無機物を押出機内で溶融混練し、これを押出機の先に取付けた口金の孔から押出してペレット化し、発泡性ポリスチレン系樹脂粒子とする方法がある。
しかし、この方法では使用できる発泡剤が比較的高沸点のものであるため、家電等の梱包材や魚箱等の食品容器に用いられる低密度のものが得にくいという課題があった。
In Patent Documents 1 and 2, a thermoplastic resin recovered from a waste product, in particular, a polystyrene resin, a foaming agent, talc, and the like are melt-kneaded in an extruder, and this is added from a hole in a die attached to the tip of the extruder. It describes a method (in-water hot-cut method) in which it is extruded into a pressurized liquid and simultaneously cut and cooled to suppress foaming to form expandable particles.
In addition, it has been studied to contain an inorganic substance in order to reinforce the properties of the polystyrene resin foam molded article. As one means, the polystyrene resin and the inorganic substance are melt-kneaded in an extruder and attached to the tip of the extruder. For example, there is a method of extruding from a hole in the die and pelletizing it to obtain expandable polystyrene resin particles.
However, since the foaming agent that can be used in this method has a relatively high boiling point, there is a problem that it is difficult to obtain a low-density one that is used in packaging materials for home appliances and food containers such as fish boxes.

この解決手段として、押出機にてポリスチレン系樹脂を造粒し、水性媒体中で比較的低沸点の発泡剤を含有させて発泡性ポリスチレン系樹脂粒子とする方法が、低密度化には非常に有用であり今後、増加すると考えられる。
ところが、こうして得られた発泡性ポリスチレン系樹脂粒子は、製造後に長期保管したものを予備発泡すると、保管前のものを予備発泡した予備発泡粒子と比べ、予備発泡粒子中の気泡が細かくなり、良好な成形体を得ることができなくなるために、長期間保管できず、保管可能期間が短いという課題が残されていた。
原因としては、発泡性ポリスチレン系樹脂粒子の気泡が保管日数の経過に従って小さくなり、気泡膜が薄くなることから成形時の耐熱性が低下する為と考えられる。
As a solution to this problem, a method of granulating a polystyrene resin with an extruder and adding a foaming agent having a relatively low boiling point in an aqueous medium to obtain expandable polystyrene resin particles is very effective for reducing the density. It is useful and will increase in the future.
However, the foamable polystyrene resin particles obtained in this way are good when pre-foamed after long-term storage after production, compared to pre-foamed particles pre-foamed before storage, resulting in finer bubbles in the pre-foamed particles. As a result, it becomes impossible to obtain a molded article, and there is a problem that it cannot be stored for a long period of time and the storage period is short.
The cause is thought to be that the heat resistance at the time of molding is lowered because the bubbles of the expandable polystyrene resin particles become smaller with the passage of storage days and the bubble film becomes thinner.

この解決手段として、特許文献3には、押出機内でカーボンブラックとポリスチレン系樹脂を混合し、カーボン含有ペレットをした後に発泡剤を含浸してカーボンブラック含有ポリスチレン系樹脂粒子を得る際に少なくとも0.5質量%の付着水分の存在下で保管する方法が開示されている。   As a means for solving this problem, Patent Document 3 discloses that at least 0. 0 is obtained when carbon black and polystyrene resin are mixed in an extruder, carbon-containing pellets are formed, and then a foaming agent is impregnated to obtain carbon black-containing polystyrene resin particles. A method of storing in the presence of 5% by weight attached moisture is disclosed.

特開平6−298983号公報JP-A-6-298893 特開平10−130420号公報Japanese Patent Laid-Open No. 10-130420 特開昭61−171746号公報JP-A 61-171746

しかしながら、特許文献3に開示された方法では、付着水分が多い為に予備発泡時において発泡性ポリスチレン系樹脂粒子間の発泡ばらつきが大きくなり、生産物の品質が安定せず、予備発泡粒子の不良率が高くなり、生産上好ましくなかった。また、予備発泡直前に脱水乾燥を行い付着水分のない状態にして予備発泡することも考えられるが、作業が煩雑になり、生産上好ましくなかった。   However, in the method disclosed in Patent Document 3, since there is a large amount of moisture adhering, the foaming variation between the expandable polystyrene resin particles becomes large at the time of prefoaming, the quality of the product is not stable, and the prefoamed particles are defective. The rate was high, which was not preferable for production. Further, it may be possible to perform dehydration and drying immediately before the prefoaming to make the prefoaming in a state where there is no adhering moisture, but the operation becomes complicated, which is not preferable in production.

本発明は、前記課題に鑑みてなされ、予備発泡時の発泡ばらつきが小さく、発泡性ポリスチレン系樹脂粒子の保管可能期間を延長でき、長時間保存品であっても良好な発泡成形体を製造可能な発泡性ポリスチレン系樹脂粒子の提供を目的とする。   The present invention has been made in view of the above problems, has a small foaming variation at the time of pre-foaming, can extend the storage period of expandable polystyrene resin particles, and can produce a good foamed molded article even if it is stored for a long time An object of the present invention is to provide expandable polystyrene resin particles.

前記目的を達成するため、本発明は、ポリスチレン系樹脂粒子に発泡剤を含有させてなる発泡性ポリスチレン系樹脂粒子であって、付着水分量が0.05〜0.45質量%の範囲であることを特徴とする発泡性ポリスチレン系樹脂粒子を提供する。   In order to achieve the above-mentioned object, the present invention is an expandable polystyrene resin particle obtained by adding a foaming agent to a polystyrene resin particle, and the moisture content is in the range of 0.05 to 0.45% by mass. An expandable polystyrene resin particle is provided.

また本発明は、ガラス転移点以下まで冷却されたポリスチレン系樹脂を少なくとも1回以上の溶融混練工程、及び溶融混練されたポリスチレン系樹脂を少なくとも1回以上のガラス転移点以下までの冷却工程を経たポリスチレン系樹脂粒子に発泡剤を含有させてなる発泡性ポリスチレン系樹脂粒子であって、付着水分量が0.05〜0.45質量%の範囲であることを特徴とする発泡性ポリスチレン系樹脂粒子を提供する。   In the present invention, the polystyrene resin cooled to the glass transition point or lower is subjected to at least one melt kneading step, and the melt-kneaded polystyrene resin is subjected to the cooling step to at least one glass transition point or lower. Expandable polystyrene resin particles obtained by adding a foaming agent to polystyrene resin particles and having a moisture content in the range of 0.05 to 0.45% by mass. I will provide a.

また本発明は、ガラス転移点以下まで冷却されたポリスチレン系樹脂を少なくとも1回以上の溶融混練工程、及び溶融混練されたポリスチレン系樹脂を少なくとも1回以上のガラス転移点以下までの冷却工程を経たポリスチレン系樹脂粒子を種粒子とし、該種粒子を水中に分散させてなる分散液中に、種粒子100質量部に対してスチレン系モノマー10〜800質量部を供給し、スチレン系モノマーを種粒子に吸収、重合させて種粒子を成長させ、成長後または成長途中で発泡剤を含有させてなる発泡性ポリスチレン系樹脂粒子であって、付着水分量が0.05〜0.45質量%の範囲であることを特徴とする発泡性ポリスチレン系樹脂粒子を提供する。   In the present invention, the polystyrene resin cooled to the glass transition point or lower is subjected to at least one melt kneading step, and the melt-kneaded polystyrene resin is subjected to the cooling step to at least one glass transition point or lower. 10 to 800 parts by mass of styrene monomer is supplied to 100 parts by mass of seed particles in a dispersion obtained by using polystyrene resin particles as seed particles and the seed particles are dispersed in water. Expandable polystyrene-based resin particles containing seeds grown by absorption and polymerization, and containing a foaming agent after growth or during growth, and a moisture content in the range of 0.05 to 0.45% by mass An expandable polystyrene resin particle is provided.

前記発泡性ポリスチレン系樹脂粒子において、粒子表面付近にヒドロキシ脂肪酸アマイドを0.05〜0.50質量%の範囲で存在させたことが好ましい。   In the expandable polystyrene resin particles, it is preferable that hydroxy fatty acid amide is present in the vicinity of the particle surface in a range of 0.05 to 0.50 mass%.

本発明の発泡性ポリスチレン系樹脂粒子において、前記ポリスチレン系樹脂粒子が廃品から回収されたポリスチレン系樹脂を含むことが好ましい。   In the expandable polystyrene resin particles of the present invention, the polystyrene resin particles preferably include a polystyrene resin recovered from a waste product.

本発明の発泡性ポリスチレン系樹脂粒子において、金属酸化物を0.1〜10.0質量%の範囲で含有することが好ましい。
前記金属酸化物は、鱗片状珪酸塩であることが好ましい。
あるいは、前記金属酸化物は、二酸化チタンであってもよい。
The expandable polystyrene resin particles of the present invention preferably contain a metal oxide in the range of 0.1 to 10.0% by mass.
The metal oxide is preferably scaly silicate.
Alternatively, the metal oxide may be titanium dioxide.

また本発明は、前記発泡性ポリスチレン系樹脂粒子を予備発泡させて得られたポリスチレン系樹脂予備発泡粒子を提供する。   The present invention also provides polystyrene resin pre-expanded particles obtained by pre-expanding the expandable polystyrene resin particles.

また本発明は、前記ポリスチレン系樹脂予備発泡粒子を成形型内に充填し、型内発泡成形して得られたポリスチレン系樹脂発泡成形体を提供する。   The present invention also provides a polystyrene resin foam molded article obtained by filling the polystyrene resin pre-expanded particles in a mold and foam-molding in the mold.

また本発明は、ガラス転移点以下まで冷却されたポリスチレン系樹脂を少なくとも1回以上の溶融混練工程、及び溶融混練されたポリスチレン系樹脂を少なくとも1回以上のガラス転移点以下までの冷却工程を経た後のポリスチレン系樹脂粒子に発泡剤を含有させて発泡性ポリスチレン系樹脂粒子を得るとともに、得られた発泡性ポリスチレン系樹脂粒子の付着水分量を0.05〜0.45質量%の範囲に調整することを特徴とする発泡性ポリスチレン系樹脂粒子の製造方法を提供する。   In the present invention, the polystyrene resin cooled to the glass transition point or lower is subjected to at least one melt kneading step, and the melt-kneaded polystyrene resin is subjected to the cooling step to at least one glass transition point or lower. A foaming agent is added to the later polystyrene resin particles to obtain expandable polystyrene resin particles, and the amount of moisture adhering to the obtained expandable polystyrene resin particles is adjusted to a range of 0.05 to 0.45 mass%. A process for producing expandable polystyrene resin particles is provided.

また本発明は、ガラス転移点以下まで冷却されたポリスチレン系樹脂を少なくとも1回以上の溶融混練工程、及び溶融混練されたポリスチレン系樹脂を少なくとも1回以上のガラス転移点以下までの冷却工程を経た後のポリスチレン系樹脂粒子を種粒子とし、該種粒子を水中に分散させてなる分散液中に、種粒子100質量部に対してスチレン系モノマー10〜800質量部を供給し、スチレン系モノマーを種粒子に吸収、重合させて種粒子を成長させ、成長後または成長途中で発泡剤を含有させて発泡性ポリスチレン系樹脂粒子を得るとともに、得られた発泡性ポリスチレン系樹脂粒子の付着水分量を0.05〜0.45質量%の範囲に調整することを特徴とする発泡性ポリスチレン系樹脂粒子の製造方法を提供する。   In the present invention, the polystyrene resin cooled to the glass transition point or lower is subjected to at least one melt kneading step, and the melt-kneaded polystyrene resin is subjected to the cooling step to at least one glass transition point or lower. The latter polystyrene resin particles are used as seed particles, and 10 to 800 parts by mass of a styrene monomer are supplied to 100 parts by mass of the seed particles in a dispersion obtained by dispersing the seed particles in water. Seed particles are absorbed and polymerized to grow seed particles, and after or during growth, a foaming agent is contained to obtain expandable polystyrene resin particles, and the amount of moisture adhering to the obtained expandable polystyrene resin particles is determined. Provided is a method for producing expandable polystyrene resin particles, wherein the content is adjusted to a range of 0.05 to 0.45 mass%.

本発明の発泡性ポリスチレン系樹脂粒子の製造方法において、付着水分量の調整前に発泡性ポリスチレン系樹脂粒子の表面付近にヒドロキシ脂肪酸アマイドを0.05〜0.50質量%の範囲で添加することが好ましい。   In the method for producing expandable polystyrene resin particles of the present invention, hydroxy fatty acid amide is added in the range of 0.05 to 0.50 mass% in the vicinity of the surface of the expandable polystyrene resin particles before adjusting the amount of adhering moisture. Is preferred.

本発明の発泡性ポリスチレン系樹脂粒子の製造方法において、前記ポリスチレン系樹脂粒子が廃品から回収されたポリスチレン系樹脂を含むことが好ましい。   In the method for producing expandable polystyrene resin particles of the present invention, it is preferable that the polystyrene resin particles include a polystyrene resin recovered from a waste product.

本発明の発泡性ポリスチレン系樹脂粒子の製造方法において、前記発泡性ポリスチレン系樹脂粒子が金属酸化物を0.1〜10.0質量%の範囲で含有することが好ましい。
前記金属酸化物は、鱗片状珪酸塩であることが好ましい。
あるいは、前記金属酸化物は、酸化チタンであってもよい。
In the method for producing expandable polystyrene resin particles of the present invention, the expandable polystyrene resin particles preferably contain a metal oxide in a range of 0.1 to 10.0% by mass.
The metal oxide is preferably scaly silicate.
Alternatively, the metal oxide may be titanium oxide.

本発明の発泡性ポリスチレン系樹脂粒子は、予備発泡時の発泡ばらつきが小さく、保管可能期間を延長でき、長時間保存品であっても外観が美麗、且つ高い強度を有する良好な発泡成形体を製造することができる。
また、本発明によれば予備発泡直前に発泡性ポリスチレン系樹脂粒子に脱水乾燥処理を施す必要もなく、発泡ばらつきが少なくなり、生産物の不良率も大幅に改善できる。
The expandable polystyrene resin particles of the present invention have a small foam variation at the time of pre-foaming, can extend the storage period, and have a good foamed molded article having a beautiful appearance and high strength even when stored for a long time. Can be manufactured.
In addition, according to the present invention, it is not necessary to subject the expandable polystyrene resin particles to dehydration drying immediately before the preliminary foaming, variation in foaming is reduced, and the defect rate of the product can be greatly improved.

実施例1と比較例1で作製した発泡性ポリスチレン系樹脂粒子の製造後の経日と予備発泡粒子の平均粒子径との関係を示すグラフである。It is a graph which shows the relationship between the age after manufacture of the expandable polystyrene-type resin particle produced in Example 1 and Comparative Example 1, and the average particle diameter of pre-expanded particle.

本発明の発泡性ポリスチレン系樹脂粒子は、ポリスチレン系樹脂粒子に発泡剤を含有させてなる発泡性ポリスチレン系樹脂粒子において、付着水分量を0.05〜0.45質量%の範囲、より好ましくは0.1〜0.30質量%の範囲に調整したことを特徴としている。   The expandable polystyrene resin particle of the present invention is an expandable polystyrene resin particle obtained by adding a foaming agent to a polystyrene resin particle, and the moisture content is preferably in the range of 0.05 to 0.45 mass%, more preferably. It is characterized by being adjusted to a range of 0.1 to 0.30% by mass.

前記ポリスチレン系樹脂粒子の樹脂材料であるポリスチレン系樹脂としては、特に限定されず、例えば、スチレン、α−メチルスチレン、ビニルトルエン、クロロスチレン、エチルスチレン、i−プロピルスチレン、ジメチルスチレン、ブロモスチレン等のスチレン系モノマーの単独重合体又はこれらの共重合体等が挙げられ、スチレン成分を50質量%以上含有するポリスチレン系樹脂が好ましく、ポリスチレンがより好ましい。   The polystyrene resin that is a resin material of the polystyrene resin particles is not particularly limited, and examples thereof include styrene, α-methylstyrene, vinyltoluene, chlorostyrene, ethylstyrene, i-propylstyrene, dimethylstyrene, bromostyrene, and the like. Homopolymers of these styrene monomers or copolymers thereof, and the like, polystyrene resins containing 50% by mass or more of styrene components are preferred, and polystyrene is more preferred.

また、前記ポリスチレン系樹脂としては、前記スチレン系モノマーを主成分とし、このスチレン系モノマーと共重合可能なビニルモノマーとの共重合体であってもよい。このようなビニルモノマーとしては、例えば、メチル(メタ)アクリレート、エチル(メタ)アクリレート、ブチル(メタ)アクリレート、セチル(メタ)アクリレート等のアルキル(メタ)アクリレート、(メタ)アクリロニトリル、ジメチルマレエート、ジメチルフマレート、ジエチルフマレート、エチルフマレートの他、ジビニルベンゼン、アルキレングリコールジメタクリレートなどの二官能性モノマーなどが挙げられる。   The polystyrene resin may be a copolymer of the styrene monomer as a main component and a vinyl monomer copolymerizable with the styrene monomer. Examples of such vinyl monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, alkyl (meth) acrylates such as cetyl (meth) acrylate, (meth) acrylonitrile, dimethyl maleate, In addition to dimethyl fumarate, diethyl fumarate, and ethyl fumarate, bifunctional monomers such as divinylbenzene and alkylene glycol dimethacrylate are exemplified.

さらに、前記ポリスチレン系樹脂は、バージン原料、使用済みの発泡成形体のリサイクル品、または家電製品を構成していたプラスチック材料、及びそれらの混合物でも良い。   Furthermore, the polystyrene-based resin may be a virgin raw material, a recycled product of a used foamed molded product, a plastic material constituting a home appliance, or a mixture thereof.

また、前記ポリスチレン系樹脂には、鱗片状珪酸塩、例えば、カオリン、タルク、天然雲母、合成雲母、セリサイト、又、二酸化チタンなどの金属酸化物、カーボンブラック、グラファイトなどの炭素化合物、難燃剤等が含有していても良い。
そして、ポリスチレン系樹脂中における鱗片状珪酸塩、金属酸化物、炭素化合物の含有量としては、0.1〜10.0質量%、好ましくは0.3〜8.0質量%である。
The polystyrene resin includes scaly silicates such as kaolin, talc, natural mica, synthetic mica, sericite, metal oxides such as titanium dioxide, carbon compounds such as carbon black and graphite, and flame retardants. Etc. may be contained.
And as content of the scale-like silicate in a polystyrene-type resin, a metal oxide, and a carbon compound, it is 0.1-10.0 mass%, Preferably it is 0.3-8.0 mass%.

前記の含有量は下記要領で測定されたものをいう。即ち、ポリスチレン系樹脂粒子を測定試料として採取し、この測定試料の質量(灰化前測定試料の質量)を測定する。そして、測定試料を30ミリリットルの磁性ルツボ上に載置して550℃に5時間に亘って加熱し、測定試料を灰化させた上でデシケーター内に放置して冷却する。しかる後、磁性ルツボ上の灰化後の測定試料(灰化後測定試料)の質量を測定して下記式に基づいて、ポリスチレン系樹脂中の含有量を算出する。
ポリスチレン系樹脂粒子中における含有量(質量%)=100×灰化後測定試料の質量/灰化前測定試料の質量
The said content says what was measured in the following way. That is, polystyrene resin particles are collected as a measurement sample, and the mass of this measurement sample (the mass of the measurement sample before ashing) is measured. Then, the measurement sample is placed on a 30 milliliter magnetic crucible and heated to 550 ° C. for 5 hours to incinerate the measurement sample, and then left in a desiccator to cool. Thereafter, the mass of the measurement sample after ashing on the magnetic crucible (measurement sample after ashing) is measured, and the content in the polystyrene resin is calculated based on the following formula.
Content (% by mass) in polystyrene resin particles = 100 × mass of measurement sample after ashing / mass of measurement sample before ashing

本発明に使用するポリスチレン系樹脂粒子としては、形状は特に限定されないが、球状が好ましく、粒子径は、後述するポリスチレン系樹脂予備発泡粒子の金型内への充填容易性の点から、0.3〜2.0mm、好ましくは0.3〜1.4mmが好ましい。また、形状が柱状となる場合は前記の好ましい粒径に相当する体積とすることが好ましい。更に、ポリスチレン系樹脂のスチレン換算重量平均分子量(Mw)は、小さいと、発泡性ポリスチレン系樹脂粒子を発泡させて得られるポリスチレン系樹脂発泡成形体の機械的強度が低下することがある一方、大きいと、発泡性ポリスチレン系樹脂粒子の発泡性が低下し、高発泡倍率のポリスチレン系樹脂発泡成形体を得ることができない虞れがあるので、12万〜60万の範囲とするのが好ましい。   The shape of the polystyrene-based resin particles used in the present invention is not particularly limited, but a spherical shape is preferable, and the particle diameter is from the viewpoint of easy filling of the polystyrene-based resin pre-expanded particles described later into the mold. The thickness is 3 to 2.0 mm, preferably 0.3 to 1.4 mm. Further, when the shape is a columnar shape, the volume corresponding to the preferable particle diameter is preferable. Furthermore, if the polystyrene-based weight average molecular weight (Mw) of the polystyrene-based resin is small, the mechanical strength of the polystyrene-based resin foam molded article obtained by foaming the expandable polystyrene-based resin particles may be low, but large. Then, the foamability of the expandable polystyrene resin particles is lowered, and there is a possibility that a polystyrene resin foam molded article having a high expansion ratio cannot be obtained. Therefore, the range of 120,000 to 600,000 is preferable.

本発明の発泡性ポリスチレン系樹脂粒子に含有させる発泡剤としては、汎用のものが用いられ、例えば、プロパン、ブタン、ペンタンなどの脂肪族炭化水素;1,1−ジクロロ−1−フルオロエタン(HCFC−141b)、1−クロロ−1,1−ジフルオロエタン(HCFC−142b)、2−クロロ−1,1,1,2−テトラフルオロエタン(HCFC−124)、1,1,1,2−テトラフルオロエタン(HFC−134a)、1,1−ジフルオロエタン(HFC−152a)などのフロン系発泡剤が挙げられ、脂肪族炭化水素が好ましい。なお、発泡剤は単独で使用してもよいし、二種以上を併用してもよい。   As the foaming agent to be contained in the expandable polystyrene resin particles of the present invention, general-purpose ones are used, for example, aliphatic hydrocarbons such as propane, butane and pentane; 1,1-dichloro-1-fluoroethane (HCFC) -141b), 1-chloro-1,1-difluoroethane (HCFC-142b), 2-chloro-1,1,1,2-tetrafluoroethane (HCFC-124), 1,1,1,2-tetrafluoro Examples include chlorofluorocarbon blowing agents such as ethane (HFC-134a) and 1,1-difluoroethane (HFC-152a), and aliphatic hydrocarbons are preferred. In addition, a foaming agent may be used independently and may use 2 or more types together.

発泡性ポリスチレン系樹脂粒子中における発泡剤の含有量は、少ないと、発泡性ポリスチレン系樹脂粒子を用いて得られるポリスチレン系樹脂発泡成形体の高発泡倍率化が困難となることがあると共に、発泡性ポリスチレン系樹脂粒子を発泡させて得られる発泡粒子同士の熱融着が不充分となってポリスチレン系樹脂発泡成形体の外観性が低下することがある一方、多いと、発泡性ポリスチレン系樹脂粒子を用いて発泡成形した際、得られるポリスチレン系樹脂発泡成形体に収縮が生じたり或いは発泡性ポリスチレン系樹脂粒子を予備発泡させて得られるポリスチレン系樹脂予備発泡粒子中の発泡ガスの調整や発泡成形に時間を要して製造効率が低下することがあるので、2.0〜9.0質量%が好ましく、3.0〜7.0質量%がより好ましい。なお、発泡性ポリスチレン系樹脂粒子中における発泡剤の含有量は、製造直後に15℃の恒温室内に5日間放置した上で測定されたものである。   If the content of the foaming agent in the expandable polystyrene resin particles is small, it may be difficult to increase the expansion ratio of the polystyrene resin foam molded product obtained using the expandable polystyrene resin particles, and foaming may occur. The foamed polystyrene resin particles obtained by foaming the expandable polystyrene resin particles may be insufficiently heat-sealed to deteriorate the appearance of the polystyrene resin foam molded product. When foam molding is carried out, the resulting polystyrene-based resin foam molding contracts or the foamed gas in the polystyrene-based resin pre-foamed particles obtained by pre-foaming the foamable polystyrene-based resin particles is adjusted or foam-molded. Therefore, 2.0 to 9.0% by mass is preferable, and 3.0 to 7.0% by mass is more preferable. There. The content of the foaming agent in the expandable polystyrene resin particles was measured after being left in a constant temperature room at 15 ° C. for 5 days immediately after production.

本発明の発泡性ポリスチレン系樹脂粒子には、粒子の表面付近にヒドロキシ脂肪酸アマイドを0.05〜0.50質量%の範囲で添加することが好ましい。ヒドロキシ脂肪酸アマイドを0.05〜0.50質量%の範囲で添加することによって発泡性ポリスチレン系樹脂粒子表面の付着水分量を適正な範囲に調整することが容易であるだけでなく、発泡性ポリスチレン系樹脂粒子の保管中に水分が逸散することを防ぐことができる。   In the expandable polystyrene resin particles of the present invention, it is preferable to add hydroxy fatty acid amide in the range of 0.05 to 0.50% by mass near the surface of the particles. By adding hydroxy fatty acid amide in the range of 0.05 to 0.50% by mass, it is easy to adjust the moisture content on the surface of the expandable polystyrene resin particles to an appropriate range, but also expandable polystyrene. It is possible to prevent moisture from escaping during storage of the resin particles.

本発明で使用できるヒドロキシ脂肪酸アマイドとして好ましいものは、ヒドロキシステアリン酸アマイド、メチロールステアリン酸アマイド、メチロールへベン酸アマイド、エチレンビスヒドロキシステアリン酸アマイド、ヘキサメチレンビスヒドロキシステアリン酸アマイド、m―キシリレンビスヒドロキシステアリン酸アマイドが挙げられる。
ヒドロキシ脂肪酸アマイドの添加量が0.05質量%未満では、発泡性ポリスチレン系樹脂粒子の予備発泡時の平均気泡径の経日変化を抑制する効果が十分得られず、0.50質量%を超える量を添加してもその効果が頭打ちとなり、却って予備発泡時の剥離、コストアップなど問題が生じる。
Preferred hydroxy fatty acid amides that can be used in the present invention are hydroxy stearic acid amide, methylol stearic acid amide, methylol to benzoic acid amide, ethylene bishydroxy stearic acid amide, hexamethylene bishydroxy stearic acid amide, m-xylylene bishydroxy. Stearic acid amide is mentioned.
When the addition amount of hydroxy fatty acid amide is less than 0.05% by mass, the effect of suppressing the daily change of the average cell diameter at the time of preliminary foaming of the expandable polystyrene resin particles cannot be obtained sufficiently, and it exceeds 0.50% by mass. Even if the amount is added, the effect reaches a peak, and problems such as peeling at the time of preliminary foaming and cost increase occur.

本発明の発泡性ポリスチレン系樹脂粒子は、付着水分量を0.05〜0.45質量%の範囲に調整したことを特徴としている。
水性媒体中でポリスチレン系樹脂粒子に発泡剤を含浸させて得られた発泡性ポリスチレン系樹脂粒子は、水性媒体から分離して洗浄し、脱水、乾燥される。この状態において発泡性ポリスチレン系樹脂粒子の付着水分量を測定した結果、0.05質量%未満であり、0.02〜0.03質量%程度のものが多かった。
そして、このような付着水分量が少ない発泡性ポリスチレン系樹脂粒子は、製造後に保管しておくと、保管日数の経過に伴って、予備発泡時の発泡粒子の平均気泡径が小さくなる傾向が見られ(図1中の比較例1参照)、またその平均気泡径の減少に伴って、その予備発泡粒子を型内発泡成形する際の発泡性が悪化し、良好な外観及び強度を有する発泡成形体が得られなくなるため、発泡性ポリスチレン系樹脂粒子の保管可能期間が短いという問題があった。
一方、特許文献3に記載されているように、水分過多の状態で発泡性ポリスチレン系樹脂粒子を保管した場合、前述した平均気泡径の経日変化は抑制できるものの、予備発泡時の発泡ばらつきが大きくなり、予備発泡粒子の不良率が高くなる問題があった。
The expandable polystyrene resin particles of the present invention are characterized in that the amount of adhering water is adjusted to a range of 0.05 to 0.45 mass%.
Expandable polystyrene resin particles obtained by impregnating polystyrene resin particles with a foaming agent in an aqueous medium are separated from the aqueous medium, washed, dehydrated and dried. As a result of measuring the moisture content of the expandable polystyrene resin particles in this state, it was less than 0.05% by mass, and many of them were about 0.02 to 0.03% by mass.
And if such expandable polystyrene resin particles with a small amount of adhering water are stored after production, the average cell diameter of the expanded particles during pre-expanding tends to decrease with the passage of storage days. (Refer to Comparative Example 1 in FIG. 1), and as the average cell diameter is reduced, the foamability when the pre-expanded particles are subjected to in-mold foam molding deteriorates, and the foam molding has good appearance and strength. Since the body could not be obtained, there was a problem that the storage period of the expandable polystyrene resin particles was short.
On the other hand, as described in Patent Document 3, when the expandable polystyrene resin particles are stored in a state of excessive moisture, the above-described change in the average cell diameter over time can be suppressed, but the foaming variation at the time of preliminary foaming is reduced. There is a problem that the defective ratio of the pre-expanded particles is increased and the ratio is increased.

本発明の発泡性ポリスチレン系樹脂粒子は、付着水分量を0.05〜0.45質量%の範囲に調整したことによって、予備発泡時の発泡ばらつきが小さく、保管可能期間を延長でき、長時間保存品であっても外観が美麗、且つ高い強度を有する良好な発泡成形体を製造することができる。
また、予備発泡直前に発泡性ポリスチレン系樹脂粒子に脱水乾燥処理を施す必要もなく、発泡ばらつきが少なくなり、生産物の不良率も大幅に改善できる。
発泡性ポリスチレン系樹脂粒子の付着水分量が0.05質量%未満では、平均気泡径の経日変化が生じ、平均気泡径の減少に伴って、予備発泡粒子を型内発泡成形する際の発泡性が悪化し、良好な外観及び強度を有する発泡成形体が得られなくなるため、発泡性ポリスチレン系樹脂粒子の保管可能期間が短くなる。一方、付着水分量が0.45質量%を越えると、予備発泡時の発泡ばらつきが大きくなり、予備発泡粒子の不良率が高くなってしまう。
The expandable polystyrene resin particles of the present invention have a small amount of foaming variation at the time of pre-foaming and can extend the storage period by adjusting the amount of adhering moisture to a range of 0.05 to 0.45% by mass. Even if it is a preserved product, it is possible to produce a good foamed molded article having a beautiful appearance and high strength.
In addition, it is not necessary to subject the expandable polystyrene resin particles to dehydration drying immediately before the preliminary foaming, so that the foaming variation is reduced, and the defect rate of the product can be greatly improved.
If the amount of moisture adhering to the expandable polystyrene resin particles is less than 0.05% by mass, the average cell diameter changes over time, and as the average cell diameter decreases, foaming occurs when pre-expanded particles are subjected to in-mold foam molding. This deteriorates the properties and makes it impossible to obtain a foamed molded article having a good appearance and strength, so that the storage period of the expandable polystyrene resin particles is shortened. On the other hand, if the amount of adhering water exceeds 0.45% by mass, the variation in foaming at the time of pre-foaming becomes large and the defective rate of pre-foamed particles becomes high.

次に、本発明の発泡性ポリスチレン系樹脂粒子の製造方法を説明する。
発泡性ポリスチレン系樹脂粒子の材料となるポリスチレン系樹脂粒子の製造方法としては、汎用の方法が用いられ、例えば、バージン原料、回収品を押出機に供給して溶融混練し、押出機からストランド状に押出して冷却してから所定長さ毎に切断してポリスチレン系樹脂粒子を製造する方法(ストランドカット法);あるいは押出機の先に取り付けた口金の孔から水中に押し出すと同時に切断し冷却してポリスチレン系樹脂粒子を製造する方法(水中ホットカット法)などが挙げられる。また、この押出機内の樹脂に鱗片状珪酸塩や金属酸化物を分散させた後、所定長さ毎に切断してポリスチレン系樹脂粒子としても良い。
Next, the manufacturing method of the expandable polystyrene resin particle of this invention is demonstrated.
A general-purpose method is used as a method for producing polystyrene-based resin particles used as a material for the expandable polystyrene-based resin particles. For example, a virgin raw material and a recovered product are supplied to an extruder and melt-kneaded. A method for producing polystyrene resin particles by extruding to cool and then cutting into predetermined lengths (strand cut method); or extruding into water from a hole of a die attached to the tip of the extruder and simultaneously cutting and cooling And a method of producing polystyrene resin particles (in-water hot cut method). Further, after the scaly silicate or metal oxide is dispersed in the resin in the extruder, polystyrene resin particles may be cut by predetermined lengths.

また、前記にて得られたポリスチレン系樹脂粒子を種粒子として水中懸濁液中にてスチレン系モノマーをポリスチレン系樹脂種粒子中に含浸させてシード重合させるシード重合法にてポリスチレン系樹脂粒子を製造し、続いて作製したポリスチレン系樹脂粒子に前述した発泡剤を添加する方法を採用しても良い。   Further, the polystyrene resin particles are obtained by seed polymerization by impregnating a polystyrene resin seed particle with a styrene monomer in a suspension in water using the obtained polystyrene resin particle as a seed particle. You may employ | adopt the method of adding the foaming agent mentioned above to the polystyrene-type resin particle manufactured and then produced.

前記スチレン系モノマーをポリスチレン系樹脂種粒子中に吸収させ、重合させてシード重合させる際のスチレン系モノマーの添加量は、種粒子100質量部に対してスチレン系モノマー10〜800質量部の範囲である。また、好ましい範囲は50〜500質量部である。添加量が10質量部未満では、スチレン系モノマーの量および重合開始剤の量が少なすぎて、種粒子の中心部まで吸収されず種粒子中での均一なシード重合ができない。また、添加量が800質量部を超えると、シード重合に要する時間がかかりすぎて生産性が低下することに加えて、種粒子に吸収されなかったスチレン系モノマー由来の重合粉末が多量に発生し好ましくない。   The amount of the styrene monomer added when the styrene monomer is absorbed in the polystyrene resin seed particles and polymerized to be seed polymerized is in the range of 10 to 800 parts by mass of the styrene monomer with respect to 100 parts by mass of the seed particles. is there. Moreover, a preferable range is 50-500 mass parts. When the addition amount is less than 10 parts by mass, the amount of the styrene monomer and the amount of the polymerization initiator are too small, and the seed particles are not absorbed to the center of the seed particles, and uniform seed polymerization cannot be performed in the seed particles. Further, if the addition amount exceeds 800 parts by mass, it takes too much time for seed polymerization and productivity is lowered, and in addition, a large amount of polymer powder derived from styrene monomer that is not absorbed by the seed particles is generated. It is not preferable.

前記スチレン系モノマーをポリスチレン系樹脂種粒子中に含浸させてシード重合させる際に用いられる重合開始剤としては、特に限定されず、例えば、ベンゾイルパーオキサイド、ラウリルパーオキサイド、t−ブチルパーオキシベンゾエート、t−ブチルパーオキサイド、t−ブチルパーオキシピバレート、t−ブチルパーオキシイソプロピルカーボネート、t−ブチルパーオキシアセテート、2,2−t−ブチルパーオキシブタン、t−ブチルパーオキシ−3、3、5トリメチルヘキサノエート、ジーt−ブチルパーオキシヘキサハイドロテレフタレートなどの有機過酸化物やアゾビスイソブチロニトリル、アゾビスジメチルバレロニトリルなどのアゾ化合物などが挙げられ、単独で用いられても併用されてもよいが、10時間の半減期を得るための分解温度が80〜120℃にある複数種類の重合開始剤を併用することが好ましい。   The polymerization initiator used when the styrene monomer is impregnated in the polystyrene resin seed particles and seed polymerization is not particularly limited, and examples thereof include benzoyl peroxide, lauryl peroxide, t-butyl peroxybenzoate, t-butyl peroxide, t-butyl peroxypivalate, t-butyl peroxyisopropyl carbonate, t-butyl peroxyacetate, 2,2-t-butylperoxybutane, t-butylperoxy-3, 3, Examples include organic peroxides such as 5-trimethylhexanoate and di-t-butylperoxyhexahydroterephthalate, and azo compounds such as azobisisobutyronitrile and azobisdimethylvaleronitrile. 10 hours half-life It is preferable that the decomposition temperature for obtaining the combination of a plurality of types of the polymerization initiator in the 80 to 120 ° C..

そして、前記シード重合、および発泡剤を含有させる際に、スチレン系モノマーの液滴及びポリスチレン系樹脂種粒子、ポリスチレン系樹脂粒子の分散性を安定させるために懸濁安定剤を用いてもよく、このような懸濁安定剤としては、例えば、ポリビニルアルコール、メチルセルロース、ポリアクリルアミド、ポリビニルピロリドンなどの水溶性高分子や、第三リン酸カルシウム、ピロリン酸マグネシウムなどの難溶性無機化合物などが挙げられ、難溶性無機化合物を用いる場合には、アニオン界面活性剤が通常、併用される。
このようなアニオン界面活性剤としては、例えば、脂肪酸石鹸、N−アシルアミノ酸又はその塩、アルキルエーテルカルボン酸塩などのカルボン酸塩,アルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸塩、ジアルキルスルホコハク酸エステル塩、アルキルスルホ酢酸塩、α−オレフィンスルホン酸塩などのスルホン酸塩、高級アルコール硫酸エステル塩、第二級高級アルコール硫酸エステル塩、アルキルエーテル硫酸塩、ポリオキシエチレンアルキルフェニルエーテル硫酸塩などの硫酸エステル塩、アルキルエーテルリン酸エステル塩、アルキルリン酸エステル塩などのリン酸エステル塩などが挙げられる。
In addition, when the seed polymerization and the foaming agent are contained, a suspension stabilizer may be used to stabilize the dispersibility of the styrene monomer droplets and the polystyrene resin seed particles and the polystyrene resin particles, Examples of such suspension stabilizers include water-soluble polymers such as polyvinyl alcohol, methyl cellulose, polyacrylamide, and polyvinyl pyrrolidone, and poorly soluble inorganic compounds such as tricalcium phosphate and magnesium pyrophosphate. When an inorganic compound is used, an anionic surfactant is usually used in combination.
Examples of such anionic surfactants include fatty acid soaps, N-acyl amino acids or salts thereof, carboxylates such as alkyl ether carboxylates, alkylbenzene sulfonates, alkyl naphthalene sulfonates, and dialkyl sulfosuccinates. Sulfonates such as alkyl sulfoacetates, α-olefin sulfonates, higher alcohol sulfates, secondary higher alcohol sulfates, alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, etc. Examples thereof include phosphoric acid ester salts such as salts, alkyl ether phosphoric acid ester salts and alkyl phosphoric acid ester salts.

更に、発泡性ポリスチレン系樹脂粒子を発泡させて得られるポリスチレン系樹脂発泡成形体の平均気泡径を調整するために、前記シード重合の終了の5〜10分前、シード重合終了直後、又は、ポリスチレン系樹脂粒子に発泡剤を含浸させた後に、気泡調整剤をポリスチレン系樹脂粒子中に0.01〜0.8質量%となるように添加してもよい。このような気泡調整剤としては、エチレンビスステアリン酸アマイドなどのステアリン酸塩、トリグリセリン脂肪酸エステルなどが挙げられる。   Furthermore, in order to adjust the average cell diameter of the polystyrene resin foam molding obtained by foaming the expandable polystyrene resin particles, 5 to 10 minutes before the end of the seed polymerization, immediately after the end of the seed polymerization, or polystyrene After impregnating the resin-based resin particles with a foaming agent, a cell regulator may be added to the polystyrene-based resin particles so as to be 0.01 to 0.8% by mass. Examples of such air conditioners include stearates such as ethylene bis stearic acid amide and triglycerin fatty acid esters.

更に、発泡性ポリスチレン系樹脂粒子に溶剤や可塑剤を添加してもよい。このような溶剤としては、スチレン、トルエン、エチルベンゼン、キシレンなどの芳香族有機化合物、シクロヘキサン、メチルシクロヘキサンなどの環式脂肪族炭化水素、酢酸エチル、酢酸ブチルなどが挙げられる。
また、前記可塑剤としては、例えば、フタル酸エステル、グリセリンジアセトモノラウレート、グリセリントリステアレート、ジアセチル化グリセリンモノステアレートなどのグリセリン脂肪酸エステル、、ジイソブチルアジペートなどのアジピン酸エステルなどがある。
発泡性ポリスチレン系樹脂粒子中における溶剤及び可塑剤の含有量はそれぞれ、少ないと、溶剤及び可塑剤を添加した効果が発現しないことがある一方、多いと、発泡性ポリスチレン系樹脂粒子を用いて得られたポリスチレン系樹脂発泡成形体に収縮や溶けが発生して外観性などが低下することがあるので、0.1〜1.5質量%が好ましく、0.2〜1.0質量%がより好ましい。
前記溶剤及び可塑剤は、前記シード重合によってポリスチレン系樹脂種粒子を成長させてポリスチレン系樹脂粒子を製造した後にポリスチレン系樹脂粒子に含浸させるか、或いは、シード重合によるポリスチレン系樹脂種粒子の成長途上、即ち、ポリスチレン系樹脂成長粒子に含浸させる。なお、ポリスチレン系樹脂種粒子に予め溶剤や可塑剤を添加しておいてもよい。
そして、前記溶剤及び可塑剤をポリスチレン系樹脂粒子、ポリスチレン系樹脂種粒子又はポリスチレン系樹脂成長粒子に含浸させる温度としては、低いと、含浸に時間を要し、発泡性ポリスチレン系樹脂粒子の製造効率が低下することがある一方、高いと、発泡性ポリスチレン系樹脂粒子同士の合着が多量に発生することがあるので、60〜120℃が好ましく、70〜100℃がより好ましい。
Further, a solvent or a plasticizer may be added to the expandable polystyrene resin particles. Examples of such a solvent include aromatic organic compounds such as styrene, toluene, ethylbenzene, and xylene, cyclic aliphatic hydrocarbons such as cyclohexane and methylcyclohexane, ethyl acetate, and butyl acetate.
Examples of the plasticizer include glycerin fatty acid esters such as phthalic acid esters, glycerin diacetomonolaurate, glycerin tristearate, and diacetylated glycerin monostearate, and adipic acid esters such as diisobutyl adipate.
When the content of the solvent and the plasticizer in the expandable polystyrene resin particles is small, the effect of adding the solvent and the plasticizer may not be manifested. On the other hand, when the content is large, the content is obtained using the expandable polystyrene resin particles. Since the resulting polystyrene-based resin foam molded article may shrink or melt and the appearance may be reduced, 0.1 to 1.5% by mass is preferable, and 0.2 to 1.0% by mass is more preferable. preferable.
The solvent and the plasticizer are produced by growing polystyrene resin seed particles by seed polymerization to produce polystyrene resin particles, and then impregnating the polystyrene resin particles, or in the process of growing polystyrene resin seed particles by seed polymerization. That is, it is impregnated with polystyrene-based resin growing particles. A solvent or a plasticizer may be added to the polystyrene resin seed particles in advance.
And if it is low as temperature which impregnates the said solvent and a plasticizer to a polystyrene-type resin particle, a polystyrene-type resin seed particle, or a polystyrene-type resin growth particle, it will take time for an impregnation and the production efficiency of an expandable polystyrene-type resin particle will be sufficient as it. On the other hand, if it is high, a large amount of coalescence between the expandable polystyrene resin particles may occur. Therefore, 60 to 120 ° C is preferable, and 70 to 100 ° C is more preferable.

更に、本発明の発泡性ポリスチレン系樹脂粒子には、物性を損なわない範囲内において、発泡セル造核剤、充填剤、難燃剤、難燃助剤、滑剤、着色剤などを前記溶剤や可塑剤と同様の要領で適宜、添加してもよい。
前記難燃剤としては、例えば、テトラブロモシクロオクタン、ヘキサブロモシクロドデカン、トリスジブロモプロピルホスフェート、テトラブロモビスフェノールAなどが挙げられる。そして、発泡性ポリスチレン系樹脂粒子中における難燃剤の含有量としては、少ないと、発泡性ポリスチレン系樹脂粒子を用いて得られるポリスチレン系樹脂発泡成形体の難燃性が不充分なことがある一方、多いと、発泡性ポリスチレン系樹脂粒子の成形性が低下することがあるので、0.5〜1.5質量%が好ましい。
また、前記難燃助剤としては、例えば、ジクミルパーオキサイドなどの有機過酸化物が挙げられる。そして、発泡性ポリスチレン系樹脂粒子中における難燃助剤の含有量は、少ないと、難燃助剤を添加した効果が発現しないことがある一方、多いと、発泡性ポリスチレン系樹脂粒子の発泡成形性が低下することがあるので、0.05〜0.5質量%が好ましい。
Furthermore, in the expandable polystyrene resin particles of the present invention, the foamed cell nucleating agent, the filler, the flame retardant, the flame retardant aid, the lubricant, the colorant and the like are added to the solvent or plasticizer within the range not impairing the physical properties. May be added as appropriate in the same manner as described above.
Examples of the flame retardant include tetrabromocyclooctane, hexabromocyclododecane, trisdibromopropyl phosphate, tetrabromobisphenol A, and the like. When the content of the flame retardant in the expandable polystyrene resin particles is small, the flame retardancy of the polystyrene resin foam molded article obtained using the expandable polystyrene resin particles may be insufficient. If it is too much, the moldability of the expandable polystyrene resin particles may be lowered, so 0.5 to 1.5% by mass is preferable.
Examples of the flame retardant aid include organic peroxides such as dicumyl peroxide. And, if the content of the flame retardant aid in the expandable polystyrene resin particles is small, the effect of adding the flame retardant aid may not be expressed, while if large, the foam molding of the expandable polystyrene resin particles. Therefore, 0.05 to 0.5% by mass is preferable.

本発明の発泡性ポリスチレン系樹脂粒子において、前述したヒドロキシ脂肪酸アマイドを添加する場合には、添加したヒドロキシ脂肪酸アマイドがなるべく樹脂粒子の表面付近に存在するように、水性媒体中でポリスチレン系樹脂粒子に発泡剤を含浸させる工程で、発泡剤と共にヒドロキシ脂肪酸アマイドを加え、添加することが望ましい。   In the expandable polystyrene resin particles of the present invention, when the hydroxy fatty acid amide is added, the polystyrene fatty acid amide is added to the polystyrene resin particles in an aqueous medium so that the added hydroxy fatty acid amide is present as close as possible to the surface of the resin particles. In the step of impregnating the foaming agent, it is desirable to add and add the hydroxy fatty acid amide together with the foaming agent.

前述したように発泡剤を含浸させて得られた発泡性ポリスチレン系樹脂粒子は、水性媒体から分離し、十分に洗浄した後、脱水、乾燥を行う。
次に、本発明の製造方法では、得られた発泡性ポリスチレン系樹脂粒子に水を塗布し、付着水分量を0.05〜0.45質量%の範囲に調節する工程を行う。
発泡性ポリスチレン系樹脂粒子に水を塗布する方法としては、質量既知の発泡性ポリスチレン系樹脂粒子に所定量の水を加え、または噴霧し、水が発泡性ポリスチレン系樹脂粒子の表面に展着するように、粒子を軽く撹拌する方法などによって行うことができる。
As described above, the expandable polystyrene resin particles obtained by impregnating the foaming agent are separated from the aqueous medium, washed thoroughly, and then dehydrated and dried.
Next, in the production method of the present invention, a step of applying water to the obtained expandable polystyrene resin particles and adjusting the amount of adhering moisture to a range of 0.05 to 0.45 mass% is performed.
As a method of applying water to the expandable polystyrene resin particles, a predetermined amount of water is added to or sprayed on the expandable polystyrene resin particles having a known mass, and the water spreads on the surface of the expandable polystyrene resin particles. Thus, it can be performed by a method of stirring the particles lightly.

このようにして得られた発泡性ポリスチレン系樹脂粒子は、予備発泡機で予備発泡されてポリスチレン系樹脂予備発泡粒子とされる。ここで、ポリスチレン系樹脂予備発泡粒子の嵩密度は、低いと、得られるポリスチレン系樹脂発泡成形体に収縮が発生して外観性が低下したり或いはポリスチレン系樹脂発泡成形体の断熱性及び機械的強度が低下することがある一方、大きいと、得られるポリスチレン系樹脂発泡成形体の軽量性が低下することがあるので、0.01〜0.25g/cmの範囲が好ましく、0.01〜0.03g/cmの範囲がより好ましい。 The expandable polystyrene resin particles thus obtained are pre-expanded with a pre-foaming machine to form polystyrene resin pre-expanded particles. Here, if the bulk density of the polystyrene-based resin pre-expanded particles is low, the resulting polystyrene-based resin foam molded product may shrink and the appearance may deteriorate, or the heat insulation and mechanical properties of the polystyrene-based resin foam molded product may decrease. On the other hand, the strength may decrease, and if it is large, the lightweight property of the resulting polystyrene-based resin foam molded article may decrease, so the range of 0.01 to 0.25 g / cm 3 is preferable, and 0.01 to A range of 0.03 g / cm 3 is more preferable.

そして、得られたポリスチレン系樹脂予備発泡粒子は、常圧にて熟成された上で発泡成形機の成形型内に形成されたキャビティ内に充填された上で、加熱蒸気などの加熱媒体により二次発泡させられ、発泡圧によって互いに熱融着一体化して所望形状を有するポリスチレン系樹脂発泡成形体とされる。
なお、ポリスチレン系樹脂予備発泡粒子の熟成温度は、低いと、ポリスチレン系樹脂予備発泡粒子の熟成時間が長くなることがある一方、高いと、ポリスチレン系樹脂予備発泡粒子中の発泡剤が散逸して成形性が低下するので、20〜60℃が好ましい。
The obtained polystyrene resin pre-expanded particles are aged at normal pressure, filled in a cavity formed in a mold of a foam molding machine, and then heated by a heating medium such as heating steam. Next, it is foamed, and heat-fusion integrated with each other by foaming pressure to obtain a polystyrene-based resin foam molded body having a desired shape.
If the aging temperature of the polystyrene resin pre-foamed particles is low, the aging time of the polystyrene resin pre-foamed particles may be long. On the other hand, if the temperature is high, the foaming agent in the polystyrene resin pre-foamed particles is dissipated. Since a moldability falls, 20-60 degreeC is preferable.

以下、本発明の実施例を記すが、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、実施例において行った各測定の方法及び評価の基準を記しておく。
Examples of the present invention will be described below, but the present invention is not limited to the description of the following examples.
First, the measurement methods and evaluation criteria performed in the examples are described.

<付着水分量>
発泡性ポリスチレン系樹脂粒子の付着水分量の測定は下記の方法で行った。
(1)得られた発泡性ポリスチレン系樹脂粒子を約5g採取し、温度23℃、湿度50%の環境下に5分間気流乾燥し、減量(付着水分量)をW1とする。
(2)残ったサンプルを150℃にて30分加熱し、減量をW2とする。
(3)次式により付着水分量を算出する。
付着水分量(%)=(W1/W2)×100
<Moisture content>
The measurement of the amount of moisture adhering to the expandable polystyrene resin particles was performed by the following method.
(1) About 5 g of the obtained expandable polystyrene resin particles are collected and air-dried for 5 minutes in an environment of a temperature of 23 ° C. and a humidity of 50%, and the weight loss (adhesion water amount) is set to W1.
(2) The remaining sample is heated at 150 ° C. for 30 minutes, and the weight loss is set to W2.
(3) Calculate the amount of adhering moisture by the following formula.
Adhering moisture amount (%) = (W1 / W2) × 100

<予備発泡粒子の嵩密度>
予備発泡粒子の嵩密度は、JIS K6911:1995年「熱硬化性プラスチック一般試験方法」に準拠して測定されたものをいう。
先ず、ポリスチレン系樹脂予備発泡粒子を測定試料としてWg採取し、この測定試料をメスシリンダー内に自然落下させ、メスシリンダー内に落下させた測定試料の体積VcmをJIS K6911に準拠した見掛け密度測定器を用いて測定し、下記式に基づいてポリスチレン系樹脂予備発泡粒子の嵩密度を測定した。
嵩密度(g/cm)=測定試料の質量(W)/測定試料の体積(V)
<Bulk density of pre-expanded particles>
The bulk density of pre-expanded particles refers to that measured according to JIS K6911: 1995 “General Test Method for Thermosetting Plastics”.
First, Wg was collected using polystyrene resin pre-expanded particles as a measurement sample, this measurement sample was naturally dropped into a graduated cylinder, and the volume Vcm 3 of the measurement sample dropped into the graduated cylinder was measured according to JIS K6911. The bulk density of the polystyrene resin pre-expanded particles was measured based on the following formula.
Bulk density (g / cm 3 ) = mass of measurement sample (W) / volume of measurement sample (V)

<予備発泡粒子の平均気泡径>
測定装置として走査電子顕微鏡JSM−6360LV(日本電気社製)を用いた。
予備発泡粒子の中から任意に選択した10個について、剃刀刃を用いて、それぞれ粒子の中心を通る平面で二等分し、その一方の切断面の表層部を走査型電子顕微鏡を用いて、20倍(場合により100倍)に拡大した画像を撮影した。
次に、撮影した画像をA4用紙上に1画像づつ印刷した。印刷された画像から、気泡を通る曲線の長さと気泡数を計測した。
計測結果から下記式により気泡の平均弦長(t)を算出した。
平均弦長 t=線長/(気泡数×写真の倍率)
そして平均弦長(t)を用いて、次式により予備発泡粒子の断面の気泡の気泡径(D)を算出した。
D=t/0.616
さらにそれらの算術平均を予備発泡粒子の平均気泡径とした(以下、気泡径と略記する)。
<Average cell diameter of pre-expanded particles>
A scanning electron microscope JSM-6360LV (manufactured by NEC Corporation) was used as a measuring device.
About 10 arbitrarily selected from the pre-foamed particles, using a razor blade, each bisected by a plane passing through the center of the particle, the surface layer portion of one of the cut surfaces using a scanning electron microscope, Images magnified 20 times (in some cases 100 times) were taken.
Next, the captured images were printed one by one on A4 paper. From the printed image, the length of the curve passing through the bubbles and the number of bubbles were measured.
From the measurement result, the average chord length (t) of the bubbles was calculated by the following formula.
Average chord length t = Line length / (Number of bubbles x Photo magnification)
And the bubble diameter (D) of the bubble of the cross section of a pre-expanded particle was computed by following Formula using average chord length (t).
D = t / 0.616
Furthermore, the arithmetic average of them was defined as the average cell diameter of the pre-expanded particles (hereinafter abbreviated as cell diameter).

<成形性>
発泡性ポリスチレン系樹脂粒子を予備発泡機(株式会社 積水工機製作所製 SKK−70型発泡機)にて水蒸気圧0.02MPaで加熱して、嵩密度0.015g/cmとなるように予備発泡し、得られた予備発泡粒子を逆円錐状の不織布で作製された容器内で23℃、湿度50%で24時間放置した。
次に、株式会社 積水工機製作所製 ASE−3SP成形機にて下記の条件にて、寸法:300×400×50mmの板状成形体を成形し、評価を行った。
成形蒸気圧 : ケージ圧 0.06MPa
金型加熱 : 3秒
一方加熱 : 5秒
両面加熱 :15秒
水冷 : 3秒
真空冷却 : 120秒(QS成形モード)
評価基準
◎ :30日保管した発泡性ポリスチレン系樹脂粒子を上記の成形条件にて成形し、成形体の外観に隙間が少なく、美麗なもの。
× :30日保管した発泡性ポリスチレン系樹脂粒子を上記の成形条件にて成形し、成形体の外観が悪いもの。
<Moldability>
The expandable polystyrene resin particles are heated at a water vapor pressure of 0.02 MPa in a pre-foaming machine (SKK-70 type foaming machine manufactured by Sekisui Koki Co., Ltd.), so that the bulk density is 0.015 g / cm 3. The pre-expanded particles obtained after foaming were left in a container made of an inverted conical nonwoven fabric at 23 ° C. and 50% humidity for 24 hours.
Next, a plate-shaped molded body having dimensions of 300 × 400 × 50 mm was molded and evaluated using the ASE-3SP molding machine manufactured by Sekisui Koki Co., Ltd. under the following conditions.
Molding vapor pressure: Cage pressure 0.06MPa
Mold heating: 3 seconds One side heating: 5 seconds Double-sided heating: 15 seconds Water cooling: 3 seconds Vacuum cooling: 120 seconds (QS molding mode)
Evaluation Criteria A: Foamed polystyrene resin particles stored for 30 days are molded under the above molding conditions, and the appearance of the molded body is small and beautiful.
X: The foamable polystyrene resin particles stored for 30 days were molded under the above molding conditions, and the molded article had a poor appearance.

<不良率>
評価基準
◎:30日保管した発泡性ポリスチレン系樹脂粒子から上記成形条件にて50個成形し、個々の密度を測定し、成形体の密度が0.015g/cm±0.002g/cmの範囲内に50個全てある場合を良好とした。
×:30日保管した発泡性ポリスチレン系樹脂粒子から上記成形条件にて50個成形し、個々の密度を測定し、成形体の密度が0.015g/cm±0.002g/cmの範囲から外れるものが1個以上ある場合を不良とした。
<Defect rate>
Evaluation criteria A: 50 foamable polystyrene resin particles stored for 30 days were molded under the above molding conditions, and the density of each was measured. The density of the molded body was 0.015 g / cm 3 ± 0.002 g / cm 3. The case where all 50 were within the range of
X: 50 foamable polystyrene-based resin particles stored for 30 days were molded under the above molding conditions, the individual densities were measured, and the density of the molded body was in the range of 0.015 g / cm 3 ± 0.002 g / cm 3 A case in which there was one or more things that deviate from the above was regarded as defective.

<経時変化>
発泡性ポリスチレン系樹脂粒子を非透水性容器内に密封し、温度15℃、湿度50℃以下にて保管し、5日、10日、30日保管後、各日ごとに付着水分を測定すると共に、嵩密度0.015/cmとなるように予備発泡し、平均気泡径を測定した。
<Change over time>
The expandable polystyrene resin particles are sealed in a water-impermeable container and stored at a temperature of 15 ° C. and a humidity of 50 ° C. or less. After storage for 5 days, 10 days, and 30 days, the adhered moisture is measured every day. The foam was prefoamed so that the bulk density was 0.015 / cm 3, and the average cell diameter was measured.

<保存可能期間>
発泡性ポリスチレン系樹脂粒子を非透水性容器内に密閉し、温度15℃、湿度50%以下にて保管し、5日おきに嵩密度0.015g/cmとなるように予備発泡し、下記の条件にて成形を行い、評価基準で◎となる成形体が得られる最長の保管日数とした。
成形条件
成形機 : 株式会社 積水工機製作所製 ASE−3SP成形機
成形体形状 : 300×400×50mm(板状成形体)
成形体密度 : 0.015g/cm
成形蒸気圧 : ケージ圧 0.09MPa
金型加熱 : 3秒
一方加熱 : 5秒
両面加熱 :15秒
水冷 : 3秒
真空冷却 : 120秒(QS成形モード)
評価基準
◎ : 成形体の外観に隙間が少なく、美麗なもの。
<Storage period>
The expandable polystyrene resin particles are sealed in a water-impermeable container, stored at a temperature of 15 ° C. and a humidity of 50% or less, pre-foamed so that the bulk density becomes 0.015 g / cm 3 every 5 days, Molding was performed under the conditions described above, and the longest storage days for obtaining a molded product that was evaluated as ◎ on the evaluation criteria were taken.
Molding conditions Molding machine: ASE-3SP molding machine manufactured by Sekisui Koki Co., Ltd. Molded body shape: 300 × 400 × 50 mm (plate-shaped molded body)
Molded body density: 0.015 g / cm 3
Molding vapor pressure: Cage pressure 0.09 MPa
Mold heating: 3 seconds One side heating: 5 seconds Double-sided heating: 15 seconds Water cooling: 3 seconds Vacuum cooling: 120 seconds (QS molding mode)
Evaluation criteria
A: The appearance of the molded body is beautiful with few gaps.

<総合評価>
◎:保管可能日数が30日以上、成形性、不良率評価すべてが良好であるもの。
×:保管可能日数が30日未満のもの、又は、成形性と不良率のいずれかが評価×であるもの。
<Comprehensive evaluation>
A: The number of days that can be stored is 30 days or more, and the moldability and defect rate evaluation are all good.
X: The number of days that can be stored is less than 30 days, or the evaluation is x for either formability or defective rate.

[実施例1]
スチレン換算重量平均分子量が29万であるポリスチレン系樹脂を押出機に供給し、230℃にて溶融混練してからストランド状に押出し、このストランドを所定長さ(平均径0.8mm、長さ1.0mm)毎に切断して、ポリスチレン系樹脂粒子を得た。
次に、攪拌機付き耐圧重合容器に、水2000質量部、ポリスチレン系樹脂粒子1500質量部、ピロリン酸マグネシウム6質量部及びドデシルベンゼンスルホン酸カルシウム0.3質量部を供給し、攪拌しつつ70℃に加熱して分散液を作製した。
次に、重合容器内にブタン162質量部を圧入して100℃で6時間に亘って保持し、ポリスチレン系樹脂粒子中にブタンを含浸させた後、重合容器内を30℃に冷却して発泡性ポリスチレン系樹脂粒子を得た。
この発泡性ポリスチレン系樹脂粒子を脱水、乾燥後付着水分量を測定した結果、0.033質量%であった。次に粒子表面に発泡性ポリスチレン系樹脂粒子100質量部に対して0.10質量部の水を塗布した。その際の付着水分量は0.11質量%であった。
前記発泡性ポリスチレン系樹脂粒子を非透水性容器内に密封し、温度15℃、湿度50%以下にて保管し、5日、10日、30日保管後の各日ごとに付着水分量を測定すると共に、嵩密度0.015g/cmに予備発泡し、気泡径を測定し、さらに予備発泡粒子を型内発泡成形して成形性、不良率を評価した。その結果を表1に記す。
[Example 1]
A polystyrene-based resin having a styrene-converted weight average molecular weight of 290,000 is supplied to an extruder, melted and kneaded at 230 ° C., and then extruded into a strand shape. This strand has a predetermined length (average diameter 0.8 mm, length 1). .0 mm) to obtain polystyrene resin particles.
Next, 2,000 parts by mass of water, 1500 parts by mass of polystyrene-based resin particles, 6 parts by mass of magnesium pyrophosphate and 0.3 parts by mass of calcium dodecylbenzenesulfonate were supplied to a pressure-resistant polymerization vessel equipped with a stirrer, and the mixture was stirred at 70 ° C. A dispersion was prepared by heating.
Next, 162 parts by mass of butane is injected into the polymerization vessel and held at 100 ° C. for 6 hours. After impregnating butane into the polystyrene resin particles, the inside of the polymerization vessel is cooled to 30 ° C. and foamed. Polystyrene resin particles were obtained.
The foamed polystyrene resin particles were dehydrated and dried, and the amount of attached water was measured. As a result, it was 0.033% by mass. Next, 0.10 parts by mass of water was applied to the particle surface with respect to 100 parts by mass of the expandable polystyrene resin particles. The amount of moisture adhering at that time was 0.11% by mass.
The expandable polystyrene resin particles are sealed in a water-impermeable container, stored at a temperature of 15 ° C. and a humidity of 50% or less, and the amount of adhering water is measured every day after storage for 5 days, 10 days, and 30 days. At the same time, the foam was prefoamed to a bulk density of 0.015 g / cm 3 , the bubble diameter was measured, and the prefoamed particles were subjected to in-mold foam molding to evaluate moldability and defect rate. The results are shown in Table 1.

[実施例2]
スチレン換算重量平均分子量が22万である回収ポリスチレン系樹脂を使用した以外は、実施例1と同様にして発泡性ポリスチレン樹脂を得た。
この発泡性ポリスチレン系樹脂粒子を脱水、乾燥後付着水分量を測定した結果、0.029質量%であった。次に粒子表面に発泡性ポリスチレン系樹脂粒子100質量部に対して0.10質量部の水を塗布した。その際の付着水分量は0.10質量%であった。
前記発泡性ポリスチレン系樹脂粒子を非透水性容器内に密封し、温度15℃、湿度50%以下にて保管し、5日、10日、30日保管後の各日ごとに付着水分量を測定すると共に、嵩密度0.015g/cmに予備発泡し、気泡径を測定し、さらに予備発泡粒子を型内発泡成形して成形性、不良率を評価した。その結果を表1に記す。
[Example 2]
An expandable polystyrene resin was obtained in the same manner as in Example 1 except that a recovered polystyrene resin having a styrene-converted weight average molecular weight of 220,000 was used.
The expandable polystyrene resin particles were dehydrated and dried, and the amount of adhering water was measured. As a result, it was 0.029% by mass. Next, 0.10 parts by mass of water was applied to the particle surface with respect to 100 parts by mass of the expandable polystyrene resin particles. At that time, the amount of adhering water was 0.10% by mass.
The expandable polystyrene resin particles are sealed in a water-impermeable container, stored at a temperature of 15 ° C. and a humidity of 50% or less, and the amount of adhering water is measured every day after storage for 5 days, 10 days, and 30 days. At the same time, the foam was prefoamed to a bulk density of 0.015 g / cm 3 , the bubble diameter was measured, and the prefoamed particles were subjected to in-mold foam molding to evaluate moldability and defect rate. The results are shown in Table 1.

[実施例3]
脱水、乾燥までは実施例1と同様にして発泡性ポリスチレン系樹脂粒子を作製し、脱水、乾燥後に付着水分量を測定した結果、0.033質量%であった。この発泡性ポリスチレン系樹脂粒子100質量部に対して0.03質量部の水を塗布した。その際の付着水分量は0.055質量%であった。
前記発泡性ポリスチレン系樹脂粒子を非透水性容器内に密封し、温度15℃、湿度50%以下にて保管し、5日、10日、30日保管後の各日ごとに付着水分量を測定すると共に、嵩密度0.015g/cmに予備発泡し、気泡径を測定し、さらに予備発泡粒子を型内発泡成形して成形性、不良率を評価した。その結果を表1に記す。
[Example 3]
Until dehydration and drying, expandable polystyrene resin particles were produced in the same manner as in Example 1, and the amount of adhering water was measured after dehydration and drying. As a result, it was 0.033% by mass. 0.03 parts by mass of water was applied to 100 parts by mass of the expandable polystyrene resin particles. The amount of moisture adhering at that time was 0.055% by mass.
The expandable polystyrene resin particles are sealed in a water-impermeable container, stored at a temperature of 15 ° C. and a humidity of 50% or less, and the amount of adhering water is measured every day after storage for 5 days, 10 days, and 30 days. At the same time, the foam was prefoamed to a bulk density of 0.015 g / cm 3 , the bubble diameter was measured, and the prefoamed particles were subjected to in-mold foam molding to evaluate moldability and defect rate. The results are shown in Table 1.

[実施例4]
脱水、乾燥までは実施例1と同様にして発泡性ポリスチレン系樹脂粒子を作製し、脱水、乾燥後に付着水分量を測定した結果、0.033質量%であった。この発泡性ポリスチレン系樹脂粒子100質量部に対して0.45質量部の水を塗布した。その際の付着水分量は0.44質量%であった。
前記発泡性ポリスチレン系樹脂粒子を非透水性容器内に密封し、温度15℃、湿度50%以下にて保管し、5日、10日、30日保管後の各日ごとに付着水分量を測定すると共に、嵩密度0.015g/cmに予備発泡し、気泡径を測定し、さらに予備発泡粒子を型内発泡成形して成形性、不良率を評価した。その結果を表1に記す。
[Example 4]
Until dehydration and drying, expandable polystyrene resin particles were produced in the same manner as in Example 1, and the amount of adhering water was measured after dehydration and drying. As a result, it was 0.033% by mass. 0.45 parts by mass of water was applied to 100 parts by mass of the expandable polystyrene resin particles. The amount of moisture adhering at that time was 0.44% by mass.
The expandable polystyrene resin particles are sealed in a water-impermeable container, stored at a temperature of 15 ° C. and a humidity of 50% or less, and the amount of adhering water is measured every day after storage for 5 days, 10 days, and 30 days. At the same time, the foam was prefoamed to a bulk density of 0.015 g / cm 3 , the bubble diameter was measured, and the prefoamed particles were subjected to in-mold foam molding to evaluate moldability and defect rate. The results are shown in Table 1.

[実施例5]
攪拌機付き耐圧重合容器に、水2000質量部、ポリスチレン系樹脂粒子1500質量部、ピロリン酸マグネシウム6質量部及びドデシルベンゼンスルホン酸カルシウム0.3質量部、ヒドロキシステアリン酸アマイドを1.5質量部(0.10質量%)供給し、攪拌しつつ70℃に加熱した以外は、実施例1と同様にして発泡性ポリスチレン系樹脂粒子を作製した。脱水乾燥後、水を塗布せずに非透水性容器内で温度15℃、湿度50%以下にて保管した。その際の付着水分量は0.09質量%であった。
前記発泡性ポリスチレン系樹脂粒子を非透水性容器内に密封し、温度15℃、湿度50%以下にて保管し、5日、10日、30日保管後の各日ごとに付着水分量を測定すると共に、嵩密度0.015g/cmに予備発泡し、気泡径を測定し、さらに予備発泡粒子を型内発泡成形して成形性、不良率を評価した。その結果を表1に記す。
[Example 5]
In a pressure-resistant polymerization vessel with a stirrer, 2000 parts by mass of water, 1500 parts by mass of polystyrene resin particles, 6 parts by mass of magnesium pyrophosphate, 0.3 parts by mass of calcium dodecylbenzenesulfonate, and 1.5 parts by mass of hydroxystearic acid amide (0 .10 mass%) Expandable polystyrene resin particles were prepared in the same manner as in Example 1 except that the mixture was supplied and heated to 70 ° C. with stirring. After dehydration and drying, it was stored in a non-permeable container at a temperature of 15 ° C. and a humidity of 50% or less without applying water. The amount of moisture adhering at that time was 0.09% by mass.
The expandable polystyrene resin particles are sealed in a water-impermeable container, stored at a temperature of 15 ° C. and a humidity of 50% or less, and the amount of adhering water is measured every day after storage for 5 days, 10 days, and 30 days. At the same time, the foam was prefoamed to a bulk density of 0.015 g / cm 3 , the bubble diameter was measured, and the prefoamed particles were subjected to in-mold foam molding to evaluate moldability and defect rate. The results are shown in Table 1.

[実施例6]
ヒドロキシステアリン酸アマイドを0.9質量部(0.06質量%)とした以外は、実施例5と同様にして発泡性ポリスチレン系樹脂粒子を作製し、脱水、乾燥後、水を塗布せずに非透水性容器内で温度15℃、湿度50%以下にて保管した。その際の付着水分量は0.07質量%であった。
前記発泡性ポリスチレン系樹脂粒子を非透水性容器内に密封し、温度15℃、湿度50%以下にて保管し、5日、10日、30日保管後の各日ごとに付着水分量を測定すると共に、嵩密度0.015g/cmに予備発泡し、気泡径を測定し、さらに予備発泡粒子を型内発泡成形して成形性、不良率を評価した。その結果を表1に記す。
[Example 6]
Except that the hydroxy stearic acid amide was changed to 0.9 parts by mass (0.06% by mass), expandable polystyrene resin particles were prepared in the same manner as in Example 5, and after dehydration and drying, water was not applied. It was stored at a temperature of 15 ° C. and a humidity of 50% or less in a non-permeable container. The amount of moisture adhering at that time was 0.07% by mass.
The expandable polystyrene resin particles are sealed in a water-impermeable container, stored at a temperature of 15 ° C. and a humidity of 50% or less, and the amount of adhering water is measured every day after storage for 5 days, 10 days, and 30 days. At the same time, the foam was prefoamed to a bulk density of 0.015 g / cm 3 , the bubble diameter was measured, and the prefoamed particles were subjected to in-mold foam molding to evaluate moldability and defect rate. The results are shown in Table 1.

[実施例7]
ヒドロキシステアリン酸アマイドを7.5質量部(0.50質量%)とした以外は、実施例5と同様にして発泡性ポリスチレン系樹脂粒子を作製し、脱水、乾燥後、水を塗布せずに非透水性容器内で温度15℃、湿度50%以下にて保管した。その際の付着水分量は0.07質量%であった。
前記発泡性ポリスチレン系樹脂粒子を非透水性容器内に密封し、温度15℃、湿度50%以下にて保管し、5日、10日、30日保管後の各日ごとに付着水分量を測定すると共に、嵩密度0.015g/cmに予備発泡し、気泡径を測定し、さらに予備発泡粒子を型内発泡成形して成形性、不良率を評価した。その結果を表1に記す。
[Example 7]
Except that the hydroxystearic acid amide was changed to 7.5 parts by mass (0.50% by mass), expandable polystyrene resin particles were prepared in the same manner as in Example 5, and after dehydration and drying, water was not applied. It was stored at a temperature of 15 ° C. and a humidity of 50% or less in a non-permeable container. The amount of moisture adhering at that time was 0.07% by mass.
The expandable polystyrene resin particles are sealed in a water-impermeable container, stored at a temperature of 15 ° C. and a humidity of 50% or less, and the amount of adhering water is measured every day after storage for 5 days, 10 days, and 30 days. At the same time, the foam was prefoamed to a bulk density of 0.015 g / cm 3 , the bubble diameter was measured, and the prefoamed particles were subjected to in-mold foam molding to evaluate moldability and defect rate. The results are shown in Table 1.

[実施例8]
スチレン換算重量平均分子量が29万であるポリスチレン系樹脂を押出機に供給して230℃にて溶融混練して押出機からストランド状に押出し、このストランドを所定長さ毎に切断して、ポリスチレン系樹脂粒子(平均径0.8mm、長さ0.8mm)とした。
次に、攪拌機付き重合容器に、水2000質量部、ポリスチレン系樹脂粒子500質量部、ピロリン酸マグネシウム6質量部及びドデシルベンゼンスルホン酸カルシウム0.3質量部を供給して攪拌しつつ70℃に加熱して分散液を作製した。続いて、ベンゾイルパーオキサイド4.5質量部及びt−ブチルパーオキシベンゾエート1.1質量部をスチレンモノマー200質量部に溶解させ、このスチレンモノマーを全て前記分散液中に攪拌しつつ供給した。
そして、分散液中にスチレンモノマーを供給し終えてから30分経過後に分散液を90℃に加熱し、この分散液中に更にスチレンモノマー1300質量部を3時間かけて一定の供給速度で供給して、ポリスチレン系樹脂粒子を種粒子としてシード重合を行なってポリスチレン系樹脂種粒子を成長させ、全てのスチレンモノマーを供給し終えてから125℃に加熱して2時間に亘って放置した後に冷却してポリスチレン系樹脂粒子を得た。シード重合させる際のスチレンモノマーの添加量は、種粒子100質量部に対してスチレンモノマー300質量部であった。次に、ポリスチレン系樹脂粒子が分散した分散液を70℃に加熱した後、難燃剤としてテトラブロモシクロオクタン23.4質量部及び難燃助剤としてジクミルパーオキサイド5.4質量部を分散液中に供給した上で重合容器を密閉して90℃に加熱した。
続いて、重合容器内にブタン162質量部を圧入して6時間に亘って保持し、ポリスチレン系樹脂粒子中にブタンを含浸させた後、重合容器内を30℃に冷却して発泡性ポリスチレン系樹脂粒子を得た。
この発泡性ポリスチレン系樹脂粒子を脱水、乾燥後付着水分量を測定した結果、0.026質量%であった。改めて粒子表面に発泡性ポリスチレン系樹脂粒子100質量部に対して0.10質量部の水を塗布した。その際の付着水分量は0.13質量%であった。
前記発泡性ポリスチレン系樹脂粒子を非透水性容器内に密封し、温度15℃、湿度50%以下にて保管し、5日、10日、30日保管後の各日ごとに付着水分量を測定すると共に、嵩密度0.015g/cmに予備発泡し、気泡径を測定し、さらに予備発泡粒子を型内発泡成形して成形性、不良率を評価した。その結果を表1に記す。
[Example 8]
A polystyrene resin having a styrene-converted weight average molecular weight of 290,000 is supplied to an extruder, melted and kneaded at 230 ° C., extruded into a strand form from the extruder, and this strand is cut into predetermined lengths to obtain a polystyrene resin. Resin particles (average diameter 0.8 mm, length 0.8 mm) were used.
Next, 2,000 parts by mass of water, 500 parts by mass of polystyrene resin particles, 6 parts by mass of magnesium pyrophosphate and 0.3 parts by mass of calcium dodecylbenzenesulfonate are supplied to a polymerization vessel equipped with a stirrer and heated to 70 ° C. while stirring. A dispersion was prepared. Subsequently, 4.5 parts by mass of benzoyl peroxide and 1.1 parts by mass of t-butylperoxybenzoate were dissolved in 200 parts by mass of styrene monomer, and all of the styrene monomer was supplied to the dispersion while stirring.
Then, 30 minutes after supplying the styrene monomer into the dispersion, the dispersion is heated to 90 ° C., and 1300 parts by mass of styrene monomer is further supplied into the dispersion at a constant supply rate over 3 hours. Then, seed polymerization is carried out using polystyrene resin particles as seed particles to grow polystyrene resin seed particles. After supplying all styrene monomers, the mixture is heated to 125 ° C. and left for 2 hours, and then cooled. Thus, polystyrene resin particles were obtained. The amount of styrene monomer added during seed polymerization was 300 parts by mass of styrene monomer with respect to 100 parts by mass of seed particles. Next, after heating the dispersion in which the polystyrene resin particles are dispersed to 70 ° C., 23.4 parts by mass of tetrabromocyclooctane as a flame retardant and 5.4 parts by mass of dicumyl peroxide as a flame retardant aid are dispersed. Then, the polymerization vessel was sealed and heated to 90 ° C.
Subsequently, 162 parts by mass of butane was press-fitted into the polymerization vessel and held for 6 hours. After impregnating butane into the polystyrene resin particles, the inside of the polymerization vessel was cooled to 30 ° C. to expand the polystyrene foam. Resin particles were obtained.
The foamed polystyrene resin particles were dehydrated and dried, and the amount of adhering water was measured. As a result, it was 0.026% by mass. Again, 0.10 parts by mass of water was applied to the particle surface with respect to 100 parts by mass of the expandable polystyrene resin particles. The amount of moisture adhering at that time was 0.13% by mass.
The expandable polystyrene resin particles are sealed in a water-impermeable container, stored at a temperature of 15 ° C. and a humidity of 50% or less, and the amount of adhering water is measured every day after storage for 5 days, 10 days, and 30 days. At the same time, the foam was prefoamed to a bulk density of 0.015 g / cm 3 , the bubble diameter was measured, and the prefoamed particles were subjected to in-mold foam molding to evaluate moldability and defect rate. The results are shown in Table 1.

[実施例9]
スチレン換算重量平均分子量が25万であるポリスチレン系樹脂を押出機に供給して230℃にて溶融混練する際に目開きが3μmの篩を通過せず且つ目開きが5μmの篩を通過する天然雲母の含有量が5.0質量%となるように添加して押出機からストランド状に押出し、このストランドを所定長さ毎に切断して、ポリスチレン系樹脂粒子とした。
それ以外は実施例1と同様にして発泡性ポリスチレン系樹脂粒子を得た。
脱水直後の付着水分量は0.022質量%であり、改めて粒子表面に発泡性ポリスチレン系樹脂粒子100質量部に対して0.10質量部の水を塗布した。その際の付着水分量は0.15質量%であった。
前記発泡性ポリスチレン系樹脂粒子を非透水性容器内に密封し、温度15℃、湿度50%以下にて保管し、5日、10日、30日保管後の各日ごとに付着水分量を測定すると共に、嵩密度0.015g/cmに予備発泡し、気泡径を測定し、さらに予備発泡粒子を型内発泡成形して成形性、不良率を評価した。その結果を表1に記す。
[Example 9]
When a polystyrene resin having a weight average molecular weight of 250,000 in terms of styrene is supplied to an extruder and melt-kneaded at 230 ° C., it does not pass through a sieve having an opening of 3 μm, and passes through a sieve having an opening of 5 μm. It added so that content of mica might be 5.0 mass%, it extruded from the extruder in the shape of a strand, this strand was cut | disconnected for every predetermined length, and it was set as the polystyrene-type resin particle.
Otherwise, expandable polystyrene resin particles were obtained in the same manner as in Example 1.
The amount of adhering water immediately after dehydration was 0.022% by mass, and 0.10 parts by mass of water was again applied to the particle surface with respect to 100 parts by mass of the expandable polystyrene resin particles. At that time, the amount of attached water was 0.15% by mass.
The expandable polystyrene resin particles are sealed in a water-impermeable container, stored at a temperature of 15 ° C. and a humidity of 50% or less, and the amount of adhering water is measured every day after storage for 5 days, 10 days, and 30 days. At the same time, the foam was prefoamed to a bulk density of 0.015 g / cm 3 , the bubble diameter was measured, and the prefoamed particles were subjected to in-mold foam molding to evaluate moldability and defect rate. The results are shown in Table 1.

[実施例10]
脱水、乾燥までは、実施例1と同様に発泡性ポリスチレン系樹脂粒子を製造し、脱水、乾燥後に付着水分量を測定した結果、0.033質量%であった。
次にこのまま非透水性容器内で温度15℃、湿度50%以下にて保管した。
前記発泡性ポリスチレン系樹脂粒子を10日保管後、嵩密度0.015g/cmに予備発泡し、平均気泡径を測定した結果、55μmであり成形性が低下していた。そこで、改めて発泡性ポリスチレン系樹脂粒子表面に、発泡性ポリスチレン系樹脂粒子100質量部に対して0.10質量部の水を塗布した。その後に測定した付着水分量は0.11質量%であった。
その後、再度非透水性容器内で温度15℃、湿度50%以下にて保管した。5日、10日、30日保管後の各日ごとに付着水分量を測定すると共に、嵩密度0.015g/cmに予備発泡し、気泡径を測定し、さらに予備発泡粒子を型内発泡成形して成形性、不良率を評価した。その結果を表1に記す。
[Example 10]
Until dehydration and drying, expandable polystyrene resin particles were produced in the same manner as in Example 1, and the amount of adhering water was measured after dehydration and drying. As a result, it was 0.033% by mass.
Next, it was stored in a non-permeable container at a temperature of 15 ° C. and a humidity of 50% or less.
The foamable polystyrene resin particles were stored for 10 days, pre-foamed to a bulk density of 0.015 g / cm 3 , and the average cell diameter was measured. As a result, it was 55 μm and the moldability was lowered. Therefore, 0.10 parts by mass of water was again applied to the surface of the expandable polystyrene resin particles with respect to 100 parts by mass of the expandable polystyrene resin particles. The amount of adhering moisture measured thereafter was 0.11% by mass.
Thereafter, it was stored again in a water-impermeable container at a temperature of 15 ° C. and a humidity of 50% or less. The moisture content is measured every day after storage for 5 days, 10 days, and 30 days, pre-foamed to a bulk density of 0.015 g / cm 3 , the bubble diameter is measured, and the pre-foamed particles are further foamed in the mold. The moldability and defect rate were evaluated by molding. The results are shown in Table 1.

[比較例1]
脱水、乾燥までは、実施例1と同様に発泡性ポリスチレン系樹脂粒子を製造し、脱水、乾燥後に付着水分量を測定した結果、0.033質量%であった。
実施例1での水の塗布を行わず、前記発泡性ポリスチレン系樹脂粒子を非透水性容器内に密封し、温度15℃、湿度50%以下にて保管し、5日、10日、30日保管後の各日ごとに付着水分量を測定すると共に、嵩密度0.015g/cmに予備発泡し、気泡径を測定し、さらに予備発泡粒子を型内発泡成形して成形性、不良率を評価した。その結果を表1に記す。
[Comparative Example 1]
Until dehydration and drying, expandable polystyrene resin particles were produced in the same manner as in Example 1, and the amount of adhering water was measured after dehydration and drying. As a result, it was 0.033% by mass.
Without applying water in Example 1, the expandable polystyrene resin particles were sealed in a water-impermeable container, stored at a temperature of 15 ° C. and a humidity of 50% or less, 5 days, 10 days, 30 days. The amount of moisture adhering is measured every day after storage, pre-foamed to a bulk density of 0.015 g / cm 3 , the bubble diameter is measured, and the pre-foamed particles are molded by in-mold foam molding to obtain moldability and defect rate. Evaluated. The results are shown in Table 1.

[比較例2]
脱水、乾燥までは、実施例1と同様に発泡性ポリスチレン系樹脂粒子を製造し、脱水、乾燥後に付着水分を測定した結果、0.033質量%であった。この発泡性ポリスチレン系樹脂粒子100質量部に対して、0.50質量部の水を塗布した。その際の付着水分量は0.51質量%であった。
前記発泡性ポリスチレン系樹脂粒子を非透水性容器内に密封し、温度15℃、湿度50%以下にて保管し、5日、10日、30日保管後の各日ごとに付着水分量を測定すると共に、嵩密度0.015g/cmに予備発泡し、気泡径を測定し、さらに予備発泡粒子を型内発泡成形して成形性、不良率を評価した。その結果を表1に記す。
[Comparative Example 2]
Until dehydration and drying, expandable polystyrene resin particles were produced in the same manner as in Example 1, and the moisture content was measured after dehydration and drying. As a result, it was 0.033% by mass. 0.50 parts by mass of water was applied to 100 parts by mass of the expandable polystyrene resin particles. The amount of moisture adhering at that time was 0.51% by mass.
The expandable polystyrene resin particles are sealed in a water-impermeable container, stored at a temperature of 15 ° C. and a humidity of 50% or less, and the amount of adhering water is measured every day after storage for 5 days, 10 days, and 30 days. At the same time, the foam was prefoamed to a bulk density of 0.015 g / cm 3 , the bubble diameter was measured, and the prefoamed particles were subjected to in-mold foam molding to evaluate moldability and defect rate. The results are shown in Table 1.

[比較例3]
ヒドロキシステアリン酸アマイドを0.45質量部(0.03質量%)とした以外は、実施例5と同様にして発泡性ポリスチレン系樹脂粒子を製造し、脱水、乾燥後、水を塗布せずに15℃以下にて保管した。その際の付着水分量は0.025質量%であった。
前記発泡性ポリスチレン系樹脂粒子を非透水性容器内に密封し、温度15℃、湿度50%以下にて保管し、5日、10日、30日保管後の各日ごとに付着水分量を測定すると共に、嵩密度0.015g/cmに予備発泡し、気泡径を測定し、さらに予備発泡粒子を型内発泡成形して成形性、不良率を評価した。その結果を表1に記す。
[Comparative Example 3]
Except that hydroxy stearic acid amide was changed to 0.45 parts by mass (0.03% by mass), expandable polystyrene resin particles were produced in the same manner as in Example 5, and after dehydration and drying, water was not applied. Stored at 15 ° C. or lower. At that time, the amount of adhering water was 0.025% by mass.
The expandable polystyrene resin particles are sealed in a water-impermeable container, stored at a temperature of 15 ° C. and a humidity of 50% or less, and the amount of adhering water is measured every day after storage for 5 days, 10 days, and 30 days. At the same time, the foam was prefoamed to a bulk density of 0.015 g / cm 3 , the bubble diameter was measured, and the prefoamed particles were subjected to in-mold foam molding to evaluate moldability and defect rate. The results are shown in Table 1.

[比較例4]
脱水、乾燥までは、実施例1と同様に発泡性ポリスチレン系樹脂粒子を製造し、脱水、乾燥後、付着水分量を測定した結果、0.033質量%であった。この発泡性ポリスチレン系樹脂粒子を15℃、湿度80%にて5日保管した結果、付着水分量は0.036質量%であった。
前記発泡性ポリスチレン系樹脂粒子を非透水性容器内に密封し、温度15℃、湿度50%以下にて保管し、5日、10日、30日保管後の各日ごとに付着水分量を測定すると共に、嵩密度0.015g/cmに予備発泡し、気泡径を測定し、さらに予備発泡粒子を型内発泡成形して成形性、不良率を評価した。その結果を表1に記す。
[Comparative Example 4]
Until dehydration and drying, expandable polystyrene resin particles were produced in the same manner as in Example 1. After dehydration and drying, the amount of adhering water was measured, and as a result, it was 0.033% by mass. As a result of storing these expandable polystyrene resin particles at 15 ° C. and 80% humidity for 5 days, the amount of adhering water was 0.036% by mass.
The expandable polystyrene resin particles are sealed in a water-impermeable container, stored at a temperature of 15 ° C. and a humidity of 50% or less, and the amount of adhering water is measured every day after storage for 5 days, 10 days, and 30 days. At the same time, the foam was prefoamed to a bulk density of 0.015 g / cm 3 , the bubble diameter was measured, and the prefoamed particles were subjected to in-mold foam molding to evaluate moldability and defect rate. The results are shown in Table 1.

[比較例5]
脱水のみ行い乾燥を行わなかった以外は、実施例1と同様に発泡性ポリスチレン系樹脂粒子を製造し、脱水後に付着水分量を測定した結果、0.039質量%であった。
前記発泡性ポリスチレン系樹脂粒子を非透水性容器内に密封し、温度15℃、湿度50%以下にて保管し、5日、10日、30日保管後の各日ごとに付着水分量を測定すると共に、嵩密度0.015g/cmに予備発泡し、気泡径を測定し、さらに予備発泡粒子を型内発泡成形して成形性、不良率を評価した。その結果を表1に記す。
[Comparative Example 5]
Except that only dehydration was performed and drying was not performed, expandable polystyrene resin particles were produced in the same manner as in Example 1, and the amount of adhering water was measured after dehydration. As a result, it was 0.039% by mass.
The expandable polystyrene resin particles are sealed in a water-impermeable container, stored at a temperature of 15 ° C. and a humidity of 50% or less, and the amount of adhering water is measured every day after storage for 5 days, 10 days, and 30 days. At the same time, the foam was prefoamed to a bulk density of 0.015 g / cm 3 , the bubble diameter was measured, and the prefoamed particles were subjected to in-mold foam molding to evaluate moldability and defect rate. The results are shown in Table 1.

[比較例6]
脱水、乾燥までは、実施例8と同様に発泡性ポリスチレン系樹脂粒子を製造し、脱水、乾燥後に付着水分を測定した結果、0.026質量%であった。
水を塗布せずに、この発泡性ポリスチレン系樹脂粒子を非透水性容器内に密封し、温度15℃、湿度50%以下にて保管し、5日、10日、30日保管後の各日ごとに付着水分量を測定すると共に、嵩密度0.015g/cmに予備発泡し、気泡径を測定し、さらに予備発泡粒子を型内発泡成形して成形性、不良率を評価した。その結果を表1に記す。
[Comparative Example 6]
Until dehydration and drying, expandable polystyrene resin particles were produced in the same manner as in Example 8, and the moisture content was measured after dehydration and drying. As a result, it was 0.026% by mass.
Without applying water, the expandable polystyrene resin particles are sealed in a water-impermeable container and stored at a temperature of 15 ° C. and a humidity of 50% or less. Each day after storage for 5 days, 10 days, and 30 days The amount of moisture adhering to each was measured, pre-foamed to a bulk density of 0.015 g / cm 3 , the bubble diameter was measured, and the pre-foamed particles were subjected to in-mold foam molding to evaluate moldability and defect rate. The results are shown in Table 1.

Figure 2010229375
Figure 2010229375

実施例1〜9では、発泡性ポリスチレン系樹脂粒子の付着水分量を0.07〜0.44質量%の範囲に調整したことによって、30日間保管後であっても予備発泡粒子の平均気泡径の変化がほとんど無かった。また、実施例1〜9で30日間保管後の発泡性ポリスチレン系樹脂粒子は、予備発泡しさらに型内発泡成形する際の成形性が良好となり、不良率も小さく、外観や強度に優れた発泡成形体を得ることができた。   In Examples 1 to 9, by adjusting the moisture content of the expandable polystyrene resin particles to a range of 0.07 to 0.44 mass%, the average cell diameter of the pre-expanded particles even after storage for 30 days There was almost no change. In addition, the expandable polystyrene resin particles after storage for 30 days in Examples 1 to 9 have good moldability when prefoamed and further subjected to in-mold foam molding, a low defect rate, and excellent foam appearance and strength. A molded body could be obtained.

実施例10については、発泡性ポリスチレン系樹脂粒子の初期の付着水分量を0.033質量%と本発明の範囲外とし、これを保管した結果、保管10日目のものは予備発泡粒子の平均気泡径が55μmに低下して成形性が悪化した。しかし、その後、発泡性ポリスチレン系樹脂粒子に水を塗布して付着水分量0.11質量%としたところ、平均気泡径は130μmとなり、成形性も良好になった。また、これを保管した場合にも、予備発泡粒子の平均気泡径の変化がほとんど無かった。すなわち、保管経日変化によって予備発泡時の平均気泡径が小さくなった発泡性ポリスチレン系樹脂粒子に対して、水を塗布して付着水分量を本発明の範囲内とすることで、予備発泡時の平均気泡径を保管前の状態に戻し得ることが実証された。   For Example 10, the initial adhering moisture content of the expandable polystyrene resin particles was 0.033% by mass and out of the scope of the present invention. The bubble diameter was reduced to 55 μm and the moldability deteriorated. However, after that, when water was applied to the expandable polystyrene resin particles so that the amount of adhering water was 0.11% by mass, the average cell diameter was 130 μm, and the moldability was also good. Further, even when this was stored, there was almost no change in the average cell diameter of the pre-expanded particles. That is, by applying water to the expandable polystyrene resin particles whose average cell diameter at the time of pre-foaming has become smaller due to changes with storage aging, the amount of adhering water is within the scope of the present invention, so that at the time of pre-foaming It has been demonstrated that the average bubble diameter can be returned to the state before storage.

一方、比較例1のように、水を付着させず、付着水分量0.033質量%と低い状態の発泡性ポリスチレン系樹脂粒子を保管した場合には、予備発泡粒子の平均気泡径が経日と共に小さくなり、保管10日目には成形性が不良となり、良好な発泡成形体が得られなかった。
また、比較例2のように、水を多めに付着させ、水分量0.51質量%と本発明の上限値を越える水分量とした場合には、平均気泡径の経日変化は生じなくなるものの、予備発泡時の発泡ばらつきが大きくなり、予備発泡粒子の不良率が高くなった。
また、比較例3のように、発泡剤含浸時に発泡剤と共にヒドロキシ脂肪酸アマイドを0.03質量%添加した場合でも、水を付着させずに付着水分量0.025質量%と低い場合には、保管5日目、10日目では変化が見られなかったが、保管30日目では予備発泡粒子の平均気泡径が45μmに低下して成形性が悪化した。
また、比較例4のように、発泡性ポリスチレン系樹脂粒子に水を付着させず、単に高湿度条件下で保管しても、付着水分量はそれほど上昇せず、平均気泡径の経日変化を抑制することはできなかった。
また、比較例5のように、ブタン含浸後の発泡性ポリスチレン系樹脂粒子に脱水のみを施した場合、付着水分量は0.039質量%となって、本発明の付着水分量下限に達しなかった。これを保管した結果は、比較例4と同様であり、平均気泡径の経日変化を抑制することはできなかった。
また、比較例6のように、シード重合によって得られた発泡性ポリスチレン系樹脂粒子に水を付着させず、付着水分量0.026質量%と低い状態で保管した結果は、比較例1と同様であり、平均気泡径の経日変化を抑制することはできなかった。
On the other hand, as in Comparative Example 1, when the expandable polystyrene resin particles in a low state with a water content of 0.033% by mass were stored without attaching water, the average cell diameter of the pre-expanded particles was changed over time. On the 10th day of storage, the moldability was poor and a good foamed molded article could not be obtained.
Further, as shown in Comparative Example 2, when water was attached in a large amount and the water content was 0.51% by mass and the water content exceeded the upper limit of the present invention, the daily change in the average bubble diameter did not occur. The variation in foaming during prefoaming increased, and the defective rate of prefoamed particles increased.
Further, as in Comparative Example 3, even when 0.03% by mass of hydroxy fatty acid amide is added together with the foaming agent at the time of impregnation with the foaming agent, when the adhering water amount is as low as 0.025% by mass without adhering water, On the 5th and 10th days of storage, no change was observed, but on the 30th day of storage, the average cell diameter of the pre-expanded particles decreased to 45 μm and the moldability deteriorated.
Further, as in Comparative Example 4, even when the foamed polystyrene resin particles are not adhered to water and are simply stored under high-humidity conditions, the amount of adhered water does not increase so much, and the average cell diameter changes over time. It was not possible to suppress it.
Further, as in Comparative Example 5, when only dehydration was performed on the expandable polystyrene resin particles impregnated with butane, the adhering moisture amount was 0.039% by mass, which did not reach the lower limit of the adhering moisture amount of the present invention. It was. The result of storing this was the same as in Comparative Example 4, and it was not possible to suppress the daily change of the average bubble diameter.
Further, as in Comparative Example 6, the result of storing the foamed polystyrene resin particles obtained by seed polymerization in a state of low water content of 0.026% by mass without adhering water was the same as in Comparative Example 1. It was not possible to suppress the daily change of the average bubble diameter.

図1は、実施例1と比較例1で作製した発泡性ポリスチレン系樹脂粒子の製造後の経日と予備発泡粒子の平均粒子径との関係を示すグラフである。
図1の結果から、発泡性ポリスチレン系樹脂粒子に適量の水を塗布した実施例1の発泡性ポリスチレン系樹脂粒子は、水を塗布しなかった比較例1の発泡性ポリスチレン系樹脂粒子と比べ、予備発泡時の平均気泡径の経日変化を抑制することができる、という顕著な効果が得られることが分かる。
FIG. 1 is a graph showing the relationship between the time after production of expandable polystyrene resin particles produced in Example 1 and Comparative Example 1 and the average particle diameter of pre-expanded particles.
From the result of FIG. 1, the expandable polystyrene resin particles of Example 1 in which an appropriate amount of water was applied to the expandable polystyrene resin particles were compared with the expandable polystyrene resin particles of Comparative Example 1 in which water was not applied. It turns out that the remarkable effect that the daily change of the average bubble diameter at the time of preliminary foaming can be suppressed is acquired.

本発明は、発泡性ポリスチレン樹脂粒子の保管時間の経過による気泡変化が少なく、外観が美麗、且つ高い強度を有する成形体を得ることのできる発泡性ポリスチレン系樹脂粒子を提供する。本発明の発泡性ポリスチレン系樹脂粒子を予備発泡し、さらにこれを型内発泡成形して得られる発泡成形体は、食品容器や梱包,緩衝材などとして用いられる。   The present invention provides an expandable polystyrene resin particle that can obtain a molded article having a small appearance, a beautiful appearance, and a high strength, with less change of bubbles due to the passage of storage time of the expandable polystyrene resin particle. The foamed molded article obtained by pre-foaming the expandable polystyrene resin particles of the present invention and further foaming them in-mold is used as a food container, packaging, cushioning material or the like.

Claims (17)

ポリスチレン系樹脂粒子に発泡剤を含有させてなる発泡性ポリスチレン系樹脂粒子であって、付着水分量が0.05〜0.45質量%の範囲であることを特徴とする発泡性ポリスチレン系樹脂粒子。   Expandable polystyrene resin particles obtained by adding a foaming agent to polystyrene resin particles and having a moisture content in the range of 0.05 to 0.45% by mass. . ガラス転移点以下まで冷却されたポリスチレン系樹脂を少なくとも1回以上の溶融混練工程、及び溶融混練されたポリスチレン系樹脂を少なくとも1回以上のガラス転移点以下までの冷却工程を経たポリスチレン系樹脂粒子に発泡剤を含有させてなる発泡性ポリスチレン系樹脂粒子であって、付着水分量が0.05〜0.45質量%の範囲であることを特徴とする発泡性ポリスチレン系樹脂粒子。   Polystyrene resin particles that have undergone at least one melt-kneading step of the polystyrene-based resin cooled to the glass transition point or less and at least one cooling step of the melt-kneaded polystyrene-based resin to the glass transition point or less. Expandable polystyrene resin particles, which are foamable polystyrene resin particles containing a foaming agent and have a moisture content in a range of 0.05 to 0.45 mass%. ガラス転移点以下まで冷却されたポリスチレン系樹脂を少なくとも1回以上の溶融混練工程、及び溶融混練されたポリスチレン系樹脂を少なくとも1回以上のガラス転移点以下までの冷却工程を経たポリスチレン系樹脂粒子を種粒子とし、該種粒子を水中に分散させてなる分散液中に、種粒子100質量部に対してスチレン系モノマー10〜800質量部を供給し、スチレン系モノマーを種粒子に吸収、重合させて種粒子を成長させ、成長後または成長途中で発泡剤を含有させてなる発泡性ポリスチレン系樹脂粒子であって、付着水分量が0.05〜0.45質量%の範囲であることを特徴とする発泡性ポリスチレン系樹脂粒子。   Polystyrene resin particles that have undergone a melt-kneading step of at least one polystyrene-based resin cooled to a glass transition point or less, and a cooling step to at least one glass transition point or less of the melt-kneaded polystyrene resin. As seed particles, in a dispersion obtained by dispersing the seed particles in water, 10 to 800 parts by mass of a styrene monomer is supplied to 100 parts by mass of the seed particles, and the styrene monomer is absorbed and polymerized in the seed particles. Expandable polystyrene resin particles obtained by growing seed particles and containing a foaming agent after or during the growth, and the moisture content is in the range of 0.05 to 0.45% by mass. Expandable polystyrene resin particles. ポリスチレン系樹脂粒子の粒子表面付近にヒドロキシ脂肪酸アマイドを0.05〜0.50質量%存在させたことを特徴とする請求項1〜3のいずれか1項に記載の発泡性ポリスチレン系樹脂粒子。   The expandable polystyrene resin particles according to any one of claims 1 to 3, wherein 0.05 to 0.50 mass% of hydroxy fatty acid amide is present near the particle surface of the polystyrene resin particles. 前記ポリスチレン系樹脂粒子が廃品から回収されたポリスチレン系樹脂を含むことを特徴とする請求項1〜4のいずれか1項に記載の発泡性ポリスチレン系樹脂粒子。   The expandable polystyrene resin particles according to any one of claims 1 to 4, wherein the polystyrene resin particles include a polystyrene resin recovered from a waste product. 金属酸化物を0.1〜10.0質量%の範囲で含有することを特徴とする請求項1〜5のいずれか1項に記載の発泡性ポリスチレン系樹脂粒子。   The expandable polystyrene resin particles according to any one of claims 1 to 5, comprising a metal oxide in a range of 0.1 to 10.0% by mass. 前記金属酸化物が鱗片状珪酸塩であることを特徴とする請求項6に記載の発泡性ポリスチレン系樹脂粒子。   The expandable polystyrene resin particles according to claim 6, wherein the metal oxide is scaly silicate. 前記金属酸化物が二酸化チタンであることを特徴とする請求項6に記載の発泡性ポリスチレン系樹脂粒子。   The expandable polystyrene resin particles according to claim 6, wherein the metal oxide is titanium dioxide. 請求項1〜8のいずれか1項に記載の発泡性ポリスチレン系樹脂粒子を予備発泡させて得られたポリスチレン系樹脂予備発泡粒子。   Polystyrene resin pre-expanded particles obtained by pre-expanding the expandable polystyrene resin particles according to any one of claims 1 to 8. 請求項9に記載のポリスチレン系樹脂予備発泡粒子を成形型内に充填し、型内発泡成形して得られたポリスチレン系樹脂発泡成形体。   A polystyrene-based resin foam molded article obtained by filling the polystyrene-based resin pre-expanded particles according to claim 9 in a mold and foam-molding in the mold. ガラス転移点以下まで冷却されたポリスチレン系樹脂を少なくとも1回以上の溶融混練工程、及び溶融混練されたポリスチレン系樹脂を少なくとも1回以上のガラス転移点以下までの冷却工程を経た後のポリスチレン系樹脂粒子に発泡剤を含有させて発泡性ポリスチレン系樹脂粒子を得るとともに、得られた発泡性ポリスチレン系樹脂粒子の付着水分量を0.05〜0.45質量%の範囲に調整することを特徴とする発泡性ポリスチレン系樹脂粒子の製造方法。   Polystyrene resin after undergoing at least one melt-kneading step of polystyrene-based resin cooled to below the glass transition point and at least one cooling step below the glass transition point of melt-kneaded polystyrene-based resin The foaming agent is contained in the particles to obtain expandable polystyrene resin particles, and the moisture content of the obtained expandable polystyrene resin particles is adjusted to a range of 0.05 to 0.45% by mass. A method for producing expandable polystyrene resin particles. ガラス転移点以下まで冷却されたポリスチレン系樹脂を少なくとも1回以上の溶融混練工程、及び溶融混練されたポリスチレン系樹脂を少なくとも1回以上のガラス転移点以下までの冷却工程を経た後のポリスチレン系樹脂粒子を種粒子とし、該種粒子を水中に分散させてなる分散液中に、種粒子100質量部に対してスチレン系モノマー10〜800質量部を供給し、スチレン系モノマーを種粒子に吸収、重合させて種粒子を成長させ、成長後または成長途中で発泡剤を含有させて発泡性ポリスチレン系樹脂粒子を得るとともに、得られた発泡性ポリスチレン系樹脂粒子の付着水分量を0.05〜0.45質量%の範囲に調整することを特徴とする発泡性ポリスチレン系樹脂粒子の製造方法。   Polystyrene resin after undergoing at least one melt-kneading step of polystyrene-based resin cooled to below the glass transition point and at least one cooling step below the glass transition point of melt-kneaded polystyrene-based resin The particles are used as seed particles, and 10 to 800 parts by mass of a styrene monomer is supplied to 100 parts by mass of the seed particles in a dispersion obtained by dispersing the seed particles in water, and the styrene monomer is absorbed into the seed particles. The seed particles are grown by polymerization and a foaming agent is added after or during the growth to obtain expandable polystyrene resin particles, and the amount of adhering moisture of the obtained expandable polystyrene resin particles is 0.05 to 0. A method for producing expandable polystyrene resin particles, wherein the content is adjusted to a range of .45% by mass. 発泡性ポリスチレン系樹脂粒子の付着水分量を調整する前に、発泡性ポリスチレン系樹脂粒子の表面付近にヒドロキシ脂肪酸アマイドを0.05〜0.50質量%の範囲で添加することを特徴とする請求項11又は12に記載の発泡性ポリスチレン系樹脂粒子の製造方法。   Before adjusting the amount of moisture adhering to the expandable polystyrene resin particles, hydroxy fatty acid amide is added in the range of 0.05 to 0.50 mass% in the vicinity of the surface of the expandable polystyrene resin particles. Item 13. The method for producing expandable polystyrene resin particles according to Item 11 or 12. 前記ポリスチレン系樹脂粒子が廃品から回収されたポリスチレン系樹脂を含むことを特徴とする請求項11又は12に記載の発泡性ポリスチレン系樹脂粒子の製造方法。   The method for producing expandable polystyrene resin particles according to claim 11 or 12, wherein the polystyrene resin particles include a polystyrene resin recovered from a waste product. 前記発泡性ポリスチレン系樹脂粒子が金属酸化物を0.1〜10.0質量%の範囲で含有することを特徴とする請求項11〜14のいずれか1項に記載の発泡性ポリスチレン系樹脂粒子の製造方法。   The expandable polystyrene resin particle according to any one of claims 11 to 14, wherein the expandable polystyrene resin particle contains a metal oxide in a range of 0.1 to 10.0% by mass. Manufacturing method. 前記金属酸化物が鱗片状珪酸塩であることを特徴とする請求項15に記載の発泡性ポリスチレン系樹脂粒子の製造方法。   The method for producing expandable polystyrene resin particles according to claim 15, wherein the metal oxide is scaly silicate. 前記金属酸化物が二酸化チタンであることを特徴とする請求項15に記載の発泡性ポリスチレン系樹脂粒子の製造方法。   The method for producing expandable polystyrene resin particles according to claim 15, wherein the metal oxide is titanium dioxide.
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