JP6799388B2 - Method for manufacturing foamable polystyrene resin particles - Google Patents
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Description
本発明は、製造後４０日以上経過し発泡力の低下した発泡性ポリスチレン系樹脂粒子に発泡剤を再含浸する発泡性ポリスチレン系樹脂粒子の製造方法に関する。 The present invention relates to a method for producing foamable polystyrene-based resin particles, which is obtained by re-impregnating foamable polystyrene-based resin particles having reduced foaming power 40 days or more after production with a foaming agent.
発泡性ポリスチレン系樹脂粒子は、比較的安価で、特殊な方法を用いずに蒸気等で発泡成形ができ、高い緩衝・断熱の効果が得られる為、社会的に有用な材料である。得られた発泡成形体は、魚箱、農産箱、食品用容器、家電製品等の緩衝材、建材用断熱材等の幅広い用途に使用されている。 Effervescent polystyrene-based resin particles are a socially useful material because they are relatively inexpensive, can be foam-molded with steam or the like without using a special method, and have high cushioning and heat insulating effects. The obtained foam molded product is used in a wide range of applications such as fish boxes, agricultural products boxes, food containers, cushioning materials for home appliances, and heat insulating materials for building materials.
発泡性ポリスチレン系樹脂粒子は、ポリスチレンに易揮発性の炭化水素類（ブタン、ペンタンなど）を発泡剤として含浸することにより製造される。その後、発泡性ポリスチレン系樹脂粒子を蒸気等の熱媒体により加熱し、ポリスチレンの軟化と発泡剤の膨張により発泡することで、低密度で所望の形状の発泡成形体を製造することができる。従って、低密度で良好な成形体を得るには発泡剤は必要不可欠であるが、低沸点であることから在庫期間中に発泡剤が逸散してしまうため、長期間の保管したものを使用することは不可能であった。 Foamable polystyrene-based resin particles are produced by impregnating polystyrene with easily volatile hydrocarbons (butane, pentane, etc.) as a foaming agent. Then, the effervescent polystyrene-based resin particles are heated by a heat medium such as steam and foamed by softening the polystyrene and expanding the foaming agent, whereby a foamed molded product having a desired shape with a low density can be produced. Therefore, a foaming agent is indispensable to obtain a good molded product with low density, but since the foaming agent has a low boiling point, the foaming agent dissipates during the stock period, so a foaming agent stored for a long period of time is used. It was impossible to do.
発泡性ポリスチレン系樹脂粒子を長期保管するために、保管方法や保管環境（冷温保管等）が検討されてきた。また、長期保管されたものを押出機等で混錬してペレット化し、通常のポリスチレンとして再利用する方法は一般的に知られている。しかしながら、発泡性ポリスチレン系樹脂粒子として再利用した例はほぼ無かった。これは、発泡性ポリスチレン系樹脂粒子に再び発泡剤を含浸することにより、成形性や成形体の品質が悪化することから、元の品質と同等の品質を得ることの難易度の高さに由来すると考える。 In order to store the foamable polystyrene resin particles for a long period of time, a storage method and a storage environment (cold storage, etc.) have been studied. Further, a method of kneading a product stored for a long period of time with an extruder or the like to pelletize it and reusing it as ordinary polystyrene is generally known. However, there have been almost no examples of reuse as foamable polystyrene resin particles. This is due to the high degree of difficulty in obtaining the same quality as the original quality because the moldability and the quality of the molded product deteriorate by impregnating the foamable polystyrene resin particles with the foaming agent again. I think that.
かかる問題に対し特許文献１及び２では、本発明とは目的が異なるが発泡性ポリスチレン系樹脂粒子を水中に分散させ、炭素数７以下の低級脂肪族炭化水素の発泡剤を密閉容器中に添加し、発泡性ポリスチレン系樹脂粒子に着色する方法が提案されている。しかしながら、長期保管し発泡力の低下した発泡性ポリスチレン系樹脂粒子への再含浸ではないため、発泡力を回復させるには至っていなかった。 In response to this problem, Patent Documents 1 and 2 disperse effervescent polystyrene-based resin particles in water and add a foaming agent of a lower aliphatic hydrocarbon having 7 or less carbon atoms to a closed container, although the purpose is different from that of the present invention. However, a method of coloring foamable polystyrene-based resin particles has been proposed. However, since it was not re-impregnated with the foamable polystyrene-based resin particles having reduced foaming power after long-term storage, the foaming power could not be recovered.
また、特許文献３では、時間の経過とともに揮発性発泡剤が気散した場合には、発泡粒子に揮発性有機発泡剤を追加含浸することが記載されている。しかしながら、概念としてはあるものの、製造後の経過日数や、揮発分の含有量等の具体的な数値は記載されておらず、更には発泡性ポリスチレン系樹脂粒子に関するものではなかった。 Further, Patent Document 3 describes that when the volatile foaming agent disperses with the passage of time, the foamed particles are additionally impregnated with the volatile organic foaming agent. However, although it is a concept, specific numerical values such as the number of days elapsed after production and the content of volatile matter are not described, and further, it is not related to foamable polystyrene resin particles.
本発明は、長期保管され発泡剤が逸散し、発泡力が低くなった発泡性ポリスチレン系樹脂粒子に、再度発泡剤を含浸して、該発泡性ポリスチレン系樹脂粒子の発泡力を回復させる製造方法を提供するものである。 According to the present invention, the effervescent polystyrene-based resin particles that have been stored for a long period of time and the effervescent agent dissipates and the effervescent force is reduced are impregnated with the effervescent agent again to restore the effervescent force of the effervescent polystyrene-based resin particles. It provides a method.
発明者らは上記従来技術の問題点を改善するため鋭意検討した結果、再含浸の条件を精査に検討することで、成形性を損なうことなく、成形体強度等の成形体品質を維持し、発泡力を回復させた発泡性ポリスチレン系樹脂粒子を得る製造方法を見出した。 As a result of diligent studies to improve the above-mentioned problems of the prior art, the inventors carefully examined the conditions for re-impregnation to maintain the quality of the molded product such as the strength of the molded product without impairing the moldability. We have found a production method for obtaining foamable polystyrene-based resin particles having restored foaming power.
すなわち、本発明の第１は、スチレン系モノマーとブタジエンを共重合した樹脂からなる発泡性ポリスチレン系樹脂粒子であって、製造後４０日以上経過し、１５０℃、３０分乾燥した際に揮発する揮発分が０．１重量％以上６．５重量％以下である発泡性ポリスチレン系樹脂粒子に対して、発泡性ポリスチレン系樹脂粒子を１００重量部としたときに発泡剤を０．１重量部以上７．４重量部以下添加し、１５０℃、３０分乾燥した際に揮発する揮発分を６．６重量％以上８．０重量％以下と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に関する。 That is, the first aspect of the present invention is an effervescent polystyrene-based resin particle made of a resin obtained by copolymerizing a styrene-based monomer and butadiene, and volatilizes when 40 days or more have passed after production and the resin is dried at 150 ° C. for 30 minutes. 0.1 parts by weight or more of the foaming agent when the foamable polystyrene resin particles are 100 parts by weight with respect to the foamable polystyrene resin particles having a volatile content of 0.1% by weight or more and 6.5% by weight or less. Production of effervescent polystyrene-based resin particles characterized by adding 7.4 parts by weight or less and reducing the volatile content that volatilizes when dried at 150 ° C. for 30 minutes to 6.6% by weight or more and 8.0% by weight or less. Regarding the method.
本発明の第２は、密閉容器中で、発泡性ポリスチレン系樹脂粒子を水中に分散させ、次いで炭素数７以下の低級脂肪族炭化水素からなる１つ以上の発泡剤を添加することにより発泡剤を該発泡性ポリスチレン系樹脂粒子に含浸させることを特徴とする第１の発明記載の発泡性ポリスチレン系樹脂粒子の製造法に関する。 The second aspect of the present invention is to disperse effervescent polystyrene-based resin particles in water in a closed container, and then add one or more effervescent agents composed of lower aliphatic hydrocarbons having 7 or less carbon atoms. The present invention relates to a method for producing foamable polystyrene-based resin particles according to the first invention, which comprises impregnating the foamable polystyrene-based resin particles with.
本発明の第３は、発泡性ポリスチレン系樹脂粒子が、スチレン系モノマーが８５重量部部以上９８重量部以下と、ブタジエン２重量部以上１５重量部以下（スチレン系モノマーとブタジエンの合計量が１００重量部である）を共重合した樹脂であることを特徴とする第１または２の発明記載の発泡性ポリスチレン系樹脂粒子の製造法に関する。 The third aspect of the present invention is that the foamable polystyrene-based resin particles contain 85 parts by weight or more and 98 parts by weight or less of the styrene-based monomer and 2 parts by weight or more and 15 parts by weight or less of butadiene (the total amount of the styrene-based monomer and butadiene is 100). The present invention relates to the method for producing foamable polystyrene-based resin particles according to the first or second invention, which is a resin obtained by copolymerizing (part by weight).
本発明の第４は、添加する発泡剤が、少なくともノルマルペンタン及び／またはイソペンタンを含むことを特徴とする第１〜３の発明記載の発泡性ポリスチレン系樹脂粒子の製造法に関する。 A fourth aspect of the present invention relates to the method for producing foamable polystyrene-based resin particles according to the first to third inventions, wherein the foaming agent to be added contains at least normal pentane and / or isopentane.
本発明の第５は、添加する発泡剤の添加温度が９５℃以上１１５℃以下あることを特徴とする第１〜４の発明記載の発泡性ポリスチレン系樹脂粒子の製造法に関する。 Fifth of the present invention relates to the method for producing foamable polystyrene-based resin particles according to the first to fourth inventions, wherein the addition temperature of the foaming agent to be added is 95 ° C. or higher and 115 ° C. or lower.
本発明の第６は、発泡剤を添加した後、該密閉容器内を９５℃以上１１５℃以下の温度まで昇温し、１時間以上保持することを特徴とする第１〜５の発明記載の発泡性ポリスチレン系樹脂粒子の製造方法に関する。 A sixth aspect of the present invention is described in the sixth aspect of the present invention, wherein after adding the foaming agent, the temperature inside the closed container is raised to a temperature of 95 ° C. or higher and 115 ° C. or lower and held for 1 hour or longer. The present invention relates to a method for producing foamable polystyrene resin particles.
本発明によれば、長期保管された発泡性ポリスチレン系樹脂粒子の表面性の悪化や成形体強度を損なうことなく発泡力に優れた発泡性ポリスチレン系樹脂粒子の製造方法を提供することができる。 According to the present invention, it is possible to provide a method for producing foamable polystyrene-based resin particles having excellent foaming power without deteriorating the surface property of the foamable polystyrene-based resin particles stored for a long period of time or impairing the strength of the molded product.
本発明は、製造後４０日以上経過し、発泡力が低下した発泡性ポリスチレン系樹脂粒子に再び発泡剤を含浸し、発泡力を回復させた発泡性ポリスチレン系樹脂粒子を得るための製造方法である。 The present invention is a production method for obtaining foamable polystyrene-based resin particles in which foaming power has been restored by impregnating foamable polystyrene-based resin particles having reduced foaming power with a foaming agent again 40 days or more after production. is there.
本発明における発泡性ポリスチレン系樹脂粒子は、スチレン系モノマーとブタジエンを共重合した樹脂からなる発泡性ポリスチレン系樹脂粒子である。スチレン系モノマーとしては、例えば、スチレン、及び、α−メチルスチレン、パラメチルスチレン、ｔ−ブチルスチレン、クロルスチレンなどのスチレン系誘導体が挙げられる。 The effervescent polystyrene-based resin particles in the present invention are effervescent polystyrene-based resin particles made of a resin obtained by copolymerizing a styrene-based monomer and butadiene. Examples of the styrene-based monomer include styrene and styrene-based derivatives such as α-methylstyrene, paramethylstyrene, t-butylstyrene, and chlorostyrene.
さらにスチレンと共重合が可能な成分として、例えばメチルアクリレート、ブチルアクリレート、メチルメタクリレート、エチルメタクリレート、セチルメタクリレートなどのアクリル酸及びメタクリル酸のエステル、あるいはアクリロニトリル、ジメチルフマレート、エチルフマレートなどの各種単量体、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２官能性単量体も包含する。これら共重合が可能な成分をブタジエンに加え、さらに１種又は２種以上使用し共重合に供しても良い。 Further, as a component capable of copolymerizing with styrene, for example, an ester of acrylic acid and methacrylic acid such as methyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate and cetyl methacrylate, or various simple substances such as acrylonitrile, dimethyl fumarate and ethyl fumarate. It also includes difunctional monomers such as weights, divinylbenzene and alkylene glycol dimethacrylate. These copolymerizable components may be added to butadiene, and one or more of them may be used for copolymerization.
本発明における発泡性ポリスチレン系樹脂粒子は、スチレン系モノマーが８５重量部部以上９８重量部以下と、ブタジエン２重量部以上１５重量部以下（スチレン系モノマーとブタジエンの合計量が１００重量部である）を共重合した樹脂であることが好ましい。 In the foamable polystyrene-based resin particles of the present invention, the styrene-based monomer is 85 parts by weight or more and 98 parts by weight or less, and the butadiene is 2 parts by weight or more and 15 parts by weight or less (the total amount of the styrene-based monomer and butadiene is 100 parts by weight). ) Is copolymerized with the resin.
ブタジエンはスチレン系モノマーと共重合することで分子内に架橋構造を形成し、成形体の強度を向上させる役割を持つ。従い、ブタジエンが２重量部未満であると、成形体の強度が悪化する傾向にある。ブタジエンが１５重量部を超えると発泡、成形時の収縮が大きく、高倍の発泡体を得難いばかりか成形体が収縮し、表面性を損なう傾向がある。 Butadiene forms a crosslinked structure in the molecule by copolymerizing with a styrene-based monomer, and has a role of improving the strength of the molded product. Therefore, if the amount of butadiene is less than 2 parts by weight, the strength of the molded product tends to deteriorate. When butadiene exceeds 15 parts by weight, the foaming and shrinkage during molding are large, and it is difficult to obtain a foam having a high magnification, and the molded product shrinks, which tends to impair the surface property.
前記基材樹脂を発泡するための発泡剤としては、公知のものが挙げられ、例えば、プロパン、イソブタン、ノルマルブタン、イソペンタン、ノルマルペンタン、ネオペンタン等の脂肪族炭化水素類、ジフルオロエタン、テトラフルオロエタン等のオゾン破壊係数がゼロであるハイドロフルオロカーボン類等の揮発性発泡剤、空気、窒素、炭酸ガス等の無機ガス、水等があげられる。そのようにして得られた発泡粒子は金型内に充填し、スチーム等を吹き込んで加熱し発泡させることで発泡成形体とすることができる。これら発泡剤の中でも、炭素数７以下の低級脂肪族炭化水素が好ましく、更にはノルマルペンタン及びイソペンタンのいずれか、または２つを含むことが好ましい。 Examples of the foaming agent for foaming the base resin include known ones, and for example, aliphatic hydrocarbons such as propane, isobutane, normal butane, isopentane, normal pentane, neopentane, difluoroethane, tetrafluoroethane and the like. Examples include volatile foaming agents such as hydrofluorocarbons having an ozone depletion potential of zero, inorganic gases such as air, nitrogen and carbon dioxide, and water. The foamed particles thus obtained can be filled in a mold, and steam or the like is blown into the mold to heat and foam the foamed molded product. Among these foaming agents, lower aliphatic hydrocarbons having 7 or less carbon atoms are preferable, and it is preferable that any or two of normal pentane and isopentane are contained.
本願でいう揮発分とは、１５０℃、３０分で乾燥した後揮発する成分であり、揮発する成分としては、炭化水素類を始めとする発泡剤、発泡助剤、低沸点の可塑剤、残存するモノマー類等を含んでいる。実際の測定は樹脂の乾燥前後の重量差より算出され、その実測を持って揮発分と定義する。 The volatile component referred to in the present application is a component that volatilizes after being dried at 150 ° C. for 30 minutes, and the volatile component includes a foaming agent such as hydrocarbons, a foaming aid, a low boiling point plasticizer, and a residue. It contains monomers and the like. The actual measurement is calculated from the weight difference before and after drying of the resin, and the actual measurement is defined as the volatile content.
本発明における発泡性ポリスチレン系樹脂粒子は製造後４０日以上経過したものである。一般的に発泡性ポリスチレン系樹脂粒子は易揮発性の発泡剤を含浸させているため、経時変化と共に発泡剤が逸散し、発泡力が低下する。そのため、製造後４０日を越えて使用することは困難であった。本発明において、実質的には製造後４０日での揮発分は５．８重量％、６０日で５．２重量％、１８０日で４．７重量％、１年で４．５重量％程度であった。このことから、製造後１年後、若しくは２年後でも発泡力を回復させることが可能であり、場合によっては５年後でも本発明を利用することで発泡力の回復が可能である。 The foamable polystyrene-based resin particles in the present invention are 40 days or more after production. Generally, since the foamable polystyrene-based resin particles are impregnated with an easily volatile foaming agent, the foaming agent dissipates with time and the foaming power decreases. Therefore, it was difficult to use it for more than 40 days after production. In the present invention, the volatile content in 40 days after production is 5.8% by weight, 5.2% by weight in 60 days, 4.7% by weight in 180 days, and 4.5% by weight in one year. Met. From this, it is possible to recover the foaming power even after 1 year or 2 years after production, and in some cases, it is possible to recover the foaming power by using the present invention even after 5 years.
本発明において発泡力を回復させる発泡性ポリスチレン系樹脂粒子は製造後４０日以上経過したものであり、揮発分が０．１重量％以上６．５重量％以下のものである。好ましくは、１．０重量％以上６．０重量％以下である。揮発分が０．１重量％未満であると、基材樹脂の軟化点が高く発泡剤の含浸がし難くなる傾向にある。揮発分が６．５重量％を超える場合には、十分な発泡力があるため、再含浸により発泡力を回復させる必要がない。 In the present invention, the foamable polystyrene-based resin particles that restore the foaming power are those that have passed 40 days or more after production and have a volatile content of 0.1% by weight or more and 6.5% by weight or less. Preferably, it is 1.0% by weight or more and 6.0% by weight or less. When the volatile content is less than 0.1% by weight, the softening point of the base resin is high and it tends to be difficult to impregnate the foaming agent. When the volatile content exceeds 6.5% by weight, there is sufficient foaming power, so it is not necessary to restore the foaming power by re-impregnation.
本発明における発泡剤の添加量は、発泡性ポリスチレン系樹脂粒子を１００重量部としたときに、０．１重量部以上７．４重量部以下であり、好ましくは、１．０重量部以上６．０重量部以下である。発泡剤量が０．５重量部未満であると、含浸される発泡剤量が少なく発泡力を回復させるには至らない。発泡剤量が７．４重量部を超えると、成形体にした場合に張れや膨れといった三次発泡が起こり見栄えを損なうか、成形時の冷却時間が長くなり生産性が悪化する。 The amount of the foaming agent added in the present invention is 0.1 parts by weight or more and 7.4 parts by weight or less, preferably 1.0 part by weight or more and 6 parts by weight when the foamable polystyrene resin particles are 100 parts by weight. It is 0.0 parts by weight or less. If the amount of the foaming agent is less than 0.5 parts by weight, the amount of the foaming agent impregnated is small and the foaming power cannot be recovered. If the amount of the foaming agent exceeds 7.4 parts by weight, tertiary foaming such as tension and swelling may occur in the molded product to impair the appearance, or the cooling time during molding becomes long and the productivity deteriorates.
また、発泡剤の添加量は発泡性ポリスチレン系樹脂粒子１００重量部に対して、目標揮発分と含浸前の発泡性ポリスチレン系樹脂粒子の揮発分の差である。 The amount of the foaming agent added is the difference between the target volatile content and the volatile content of the foamable polystyrene resin particles before impregnation with respect to 100 parts by weight of the foamable polystyrene resin particles.
本発明における含浸後に得られる発泡性ポリスチレン系樹脂粒子の揮発分は６．６重量％以上８．０重量％以下である。揮発分が６．６重量％未満であると、再含浸後の乾燥工程等で揮発分が低くなることを考慮すると、揮発分が低くなり発泡力が低くなる。揮発分が８．０重量％を超える場合は、成形体にした場合に張れや膨れといった三次発泡が起こり見栄えを損なうか、成形時の冷却時間が長くなり生産性が悪化する。 The volatile content of the foamable polystyrene-based resin particles obtained after impregnation in the present invention is 6.6% by weight or more and 8.0% by weight or less. If the volatile content is less than 6.6% by weight, the volatile content is low and the foaming power is low, considering that the volatile content is low in the drying step after re-impregnation. When the volatile content exceeds 8.0% by weight, tertiary foaming such as tension and swelling occurs when the molded product is formed, which impairs the appearance, or the cooling time during molding becomes long and the productivity deteriorates.
本発明における発泡剤の添加温度とは発泡剤を添加するときの温度であり、９５℃以上１１５℃以下であることが好ましい。発泡剤の添加温度が９５℃未満であると、発泡剤が液状のまま添加される可能性があり、セル構造が変化し強度が悪化する傾向にある。発泡剤の添加温度が１１５℃を超えると、特に問題はないが、生産性が悪くなることからあまり好ましくない。 The addition temperature of the foaming agent in the present invention is the temperature at which the foaming agent is added, and is preferably 95 ° C. or higher and 115 ° C. or lower. If the addition temperature of the foaming agent is less than 95 ° C., the foaming agent may be added in a liquid state, and the cell structure tends to change and the strength tends to deteriorate. If the addition temperature of the foaming agent exceeds 115 ° C., there is no particular problem, but it is not so preferable because the productivity deteriorates.
本発明における発泡剤の含浸温度とは発泡剤を添加した後密閉容器内を一定時間保持するときの温度であり、９５℃以上１１５℃以下であることが好ましい。含浸温度が９５℃未満であると、発泡剤の含浸効率が悪くなり、発泡力が不足する。発泡剤の含浸温度が１１５℃を超えると、特に問題はないが、生産性が悪くなることからあまり好ましくない。 The impregnation temperature of the foaming agent in the present invention is the temperature at which the inside of the closed container is held for a certain period of time after the foaming agent is added, and is preferably 95 ° C. or higher and 115 ° C. or lower. If the impregnation temperature is less than 95 ° C., the impregnation efficiency of the foaming agent deteriorates and the foaming power becomes insufficient. If the impregnation temperature of the foaming agent exceeds 115 ° C., there is no particular problem, but it is not so preferable because the productivity deteriorates.
本発明においては、発泡剤を添加した後、密閉容器内を９５℃以上１１５℃以下の温度まで昇温し、１時間以上保持することが好ましい。１時間未満であると、発泡剤が含浸し樹脂内を拡散する時間としては短いために、含浸効率が悪化し含浸後の揮発分が低くなる傾向にある。 In the present invention, after adding the foaming agent, it is preferable to raise the temperature inside the closed container to 95 ° C. or higher and 115 ° C. or lower and hold it for 1 hour or longer. If it is less than 1 hour, the time for the foaming agent to impregnate and diffuse in the resin is short, so that the impregnation efficiency tends to deteriorate and the volatile content after impregnation tends to decrease.
本発明においては、発泡剤の圧力若しくは不活性の気体の圧力により、密閉容器内で発泡性ポリスチレン系樹脂粒子が発泡することのないようにしなければならない。発泡性ポリスチレン系樹脂粒子は、水中であっても温度が上昇し、樹脂粒子の軟化と同時に粒子内部の圧力が上昇すると発泡する。これを抑制するために、例えば、発泡剤を密閉容器内の温度以上かつ発泡剤の沸点以上に加温し、気体状態で添加する方法が挙げられる。また、密閉容器を加温する前に不活性気体を添加し、発泡性ポリスチレン系樹脂粒子内部の発泡剤の蒸気圧以上に密閉容器内の圧力を高める方法等が挙げられる。発泡を抑制するための不活性気体としては、窒素、ヘリウム等であり、好ましくは窒素である。 In the present invention, the foamable polystyrene resin particles must be prevented from foaming in the closed container due to the pressure of the foaming agent or the pressure of the inert gas. The effervescent polystyrene-based resin particles foam when the temperature rises even in water and the pressure inside the particles rises at the same time as the resin particles soften. In order to suppress this, for example, a method of heating the foaming agent to a temperature equal to or higher than the temperature in the closed container and higher than the boiling point of the foaming agent and adding the foaming agent in a gaseous state can be mentioned. Further, a method of adding an inert gas before heating the closed container to increase the pressure inside the closed container above the vapor pressure of the foaming agent inside the foamable polystyrene resin particles can be mentioned. Examples of the inert gas for suppressing foaming are nitrogen, helium and the like, preferably nitrogen.
特に、本発明の製造方法としては、密閉容器中で、発泡性ポリスチレン系樹脂粒子を水中に分散させ、次いで炭素数７以下の低級脂肪族炭化水素からなる１つ以上の発泡剤を添加することにより発泡剤を該発泡性ポリスチレン系樹脂粒子に含浸させることが好ましい。 In particular, as the production method of the present invention, foamable polystyrene-based resin particles are dispersed in water in a closed container, and then one or more foaming agents composed of lower aliphatic hydrocarbons having 7 or less carbon atoms are added. It is preferable to impregnate the foamable polystyrene resin particles with a foaming agent.
本発明の発泡性ポリスチレン系樹脂粒子に添加可能な添加物として可塑剤、造核剤、難燃剤、難燃助剤、外添剤等を、本発明の効果を阻害しない範囲で使用してもよい。 Even if a plasticizer, a nucleating agent, a flame retardant, a flame retardant, an external additive, etc. are used as additives that can be added to the foamable polystyrene resin particles of the present invention, as long as the effects of the present invention are not impaired. Good.
本発明において用いられる可塑剤としては、例えば、ジイソブチルアジペート、ジオクチルアジペート、ジブチルセバケート、グリセリントリステアレート、グリセリントリカプリレート、ヤシ油、パーム油、菜種油などが挙げられる。これら可塑剤のうちでも、医療分野あるいは直接食品に接触する包装材料分野向けに使用する場合には、食用油であるのが好ましく、さらには、やし油、パーム油、菜種油がより好ましい。 Examples of the plasticizer used in the present invention include diisobutyl adipate, dioctyl adipate, dibutyl sebacate, glycerin tristearate, glycerin tricaprelate, coconut oil, palm oil, rapeseed oil and the like. Among these plasticizers, when used in the medical field or the packaging material field in direct contact with food, edible oil is preferable, and coconut oil, palm oil, and rapeseed oil are more preferable.
本発明においては、可塑剤を、スチレン系樹脂粒子の重合工程、発泡剤を含浸させる工程、等にて添加してもよい。 In the present invention, the plasticizer may be added in a step of polymerizing styrene resin particles, a step of impregnating with a foaming agent, or the like.
本発明において用いられる造核剤としては、例えば、メタクリル酸メチル系共重合体、ポリエチレンワックス、タルク、脂肪酸ビスアマイド、エチレン−酢酸ビニル共重合体樹脂、等が挙げられる。脂肪酸ビスアマイドの具体的例としては、メチレンビスステアリルアマイド、エチレンビスステアリルアマイド、ヘキサメチレンビスパルミチン酸アマイド、エチレンビスオレイン酸アマイド等である。 Examples of the nucleating agent used in the present invention include methyl methacrylate-based copolymers, polyethylene wax, talc, fatty acid bisamide, ethylene-vinyl acetate copolymer resin, and the like. Specific examples of the fatty acid bisamide include methylene bisstearyl amide, ethylene bisstearyl amide, hexamethylene bispalmitate amide, ethylene bisoleic acid amide, and the like.
本発明において用いられる難燃剤および難燃助剤としては、公知慣用のものが使用できる。 As the flame retardant and the flame retardant aid used in the present invention, known and commonly used ones can be used.
難燃剤の具体例としては、例えば、ヘキサブロモシクロドデカン、テトラブロモブタン、ヘキサブロモシクロヘキサン等のハロゲン化脂肪族炭化水素系化合物、テトラブロモビスフェノールＡ、テトラブロモビスフェノールＦ、２，４，６−トリブロモフェノール等の臭素化フェノール類、テトラブロモビスフェノールＡ−ビス（２，３−ジブロモプロピルエーテル）、テトラブロモビスフェノールＡ−ビス（２，３−ジブロモ−２−メチルプロピルエーテル）、テトラブロモビスフェノールＡ−ジグリシジルエーテル、２，２−ビス［４'（２”，３”−ジブロモアルコキシ）−３'，５'−ジブロモフェニル］−プロパン等の臭素化フェノール誘導体、臭素化スチレン・ブタジエンブロック共重合体、臭素化ランダムスチレン・ブタジエン共重合体、臭素化スチレン・ブタジエングラフと共重合体などの臭素化ブタジエン・ビニル芳香族炭化水素共重合体（例えば、Ｃｈｅｍｔｕｒａ社製ＥＭＥＲＡＬＤ３０００、若しくは、特表２００９−５１６０１９号公報に開示されている）などが挙げられる。これら難燃剤は、単独で用いてもよいし、２種以上を混合して用いてもよい。 Specific examples of the flame retardant include halogenated aliphatic hydrocarbon compounds such as hexabromocyclododecane, tetrabromobutane, and hexabromocyclohexane, tetrabromobisphenol A, tetrabromobisphenol F, 2,4,6-tri. Brominated phenols such as bromophenol, tetrabromobisphenol A-bis (2,3-dibromopropyl ether), tetrabromobisphenol A-bis (2,3-dibromo-2-methylpropyl ether), tetrabromobisphenol A- Brominated phenol derivatives such as diglycidyl ether, 2,2-bis [4'(2 ", 3" -dibromoalkoxy) -3', 5'-dibromophenyl] -propane, brominated styrene-butadiene block copolymer , Brobroinated random styrene / butadiene copolymer, brominated butadiene / vinyl aromatic hydrocarbon copolymer such as brominated styrene / butadiene graph and copolymer (for example, EMERALD3000 manufactured by Chemtura, or Special Table 2009-516019. Disclosed in the Gazette) and the like. These flame retardants may be used alone or in combination of two or more.
難燃助剤の具体例としては、例えば、クメンハイドロパーオキサイド、ジクミルパーオキサイド、ｔ−ブチルハイドロパーオキサイド、２，３−ジメチルー２，３−ジフェニルブタン等の開始剤を使用してもよい。 As specific examples of the flame retardant aid, for example, an initiator such as cumene hydroperoxide, dicumyl peroxide, t-butyl hydroperoxide, 2,3-dimethyl-2,3-diphenylbutane may be used. ..
外添剤の具体例としては、例えば、ラウリン酸トリグリセライド、ステアリン酸トリグリセライド、リノール酸トリグリセライドなどの脂肪酸トリグリセライド、ラウリン酸ジグリセライド、ステアリン酸ジグリセライド、リノール酸ジグリセライドなどの脂肪酸ジグリセライド、ラウリン酸モノグリセライド、ステアリン酸モノグリセライド、リノール酸モノグリセライドなどの脂肪酸モノグリセライド、ステアリン酸亜鉛、ステアリン酸カルシウム、ステアリン酸マグネシウム、ステアリン酸アルミニウム、ラウリン酸亜鉛、ラウリン酸カルシウムなどの脂肪酸金属塩、ポリオキシエチレンセチルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンラウレート、ポリオキシエチレンパルミテート、ポリオキシエチレンステアレート、ポリオキシエチレンオレエート等の非イオン界面活性剤などが挙げられる。これら外添剤及び添付剤は単独で用いても良いし、２種以上を混合しても良い。また、これら外添剤及び添付剤は発泡剤含浸時に水系に添加してもよいし、脱水後に若しくは乾燥後に添加し被覆してもよく、被覆方法によらない。好ましい被覆方法は、乾燥後に添付し、混合撹拌することにより被覆する方法である。 Specific examples of the external preparation include fatty acid triglycerides such as triglyceride laurate, triglyceride stearate, and triglyceride linoleic acid, diglyceride laurate, diglyceride stearate, diglyceride linoleic acid, monoglyceride laurate, and monoglyceride stearate. , Fatty acid monoglyceride such as linoleic acid monoglyceride, fatty acid metal salts such as zinc stearate, calcium stearate, magnesium stearate, aluminum stearate, zinc laurate, calcium laurate, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxy Examples thereof include nonionic surfactants such as ethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene palmitate, polyoxyethylene stearate, and polyoxyethylene oleate. These external additives and attachments may be used alone or in combination of two or more. Further, these external additives and attachments may be added to the water system when impregnated with the foaming agent, or may be added and coated after dehydration or drying, regardless of the coating method. A preferred coating method is a method of coating by attaching after drying and mixing and stirring.
本発明の発泡性ポリスチレン系樹脂粒子は、公知の方法で発泡させて、ポリスチレン系樹脂発泡成形体を得ることが出来る。例えば、一旦予備発泡粒子を作製し、その後型に該予備発泡粒子を充填し成形する方法や、発泡性ポリスチレン系樹脂粒子を直接型に充填し発泡成型する方法等が挙げられる。発泡成形体の製造方法の例としては下記のような方法が挙げられる。本発明の発泡性ポリスチレン系樹脂粒子を回転攪拌式予備発泡装置で、水蒸気を用いて８０〜１１０℃程度で加熱することにより、嵩倍率が３０〜１００ｍｌ／ｇ程度の予備発泡粒を得、得られた予備発泡粒子を所望の形状の金型内に充填し、水蒸気などを用いて１０５〜１４５℃程度で加熱することによりポリスチレン系樹脂発泡成形体とすることができる。 このようにして得られた、本発明のポリスチレン系樹脂発泡成形体は、難燃性を有し、且つ残存スチレン系単量体量も少ないものとなる。 The foamable polystyrene-based resin particles of the present invention can be foamed by a known method to obtain a polystyrene-based resin foam molded product. For example, a method of preparing pre-foamed particles once and then filling the mold with the pre-foamed particles for molding, a method of directly filling the mold with foamable polystyrene resin particles and foam-molding, and the like can be mentioned. Examples of the method for producing a foam molded product include the following methods. By heating the effervescent polystyrene-based resin particles of the present invention with a rotary stirring type pre-foaming device at about 80 to 110 ° C., pre-foamed particles having a bulk ratio of about 30 to 100 ml / g can be obtained. The polystyrene-based resin foam molded product can be obtained by filling the obtained pre-foamed particles in a mold having a desired shape and heating the molded product at about 105 to 145 ° C. using steam or the like. The polystyrene-based resin foam molded product of the present invention thus obtained has flame retardancy and a small amount of residual styrene-based monomer.
以下に、実施例および比較例を挙げるが、本発明は、これらによって制限されるものではない。 なお、測定評価法は、以下の通りに実施した。 Examples and comparative examples are given below, but the present invention is not limited thereto. The measurement and evaluation method was carried out as follows.
（揮発分測定）
乾燥機：送風定温乾燥機（東京理化器械株式会社製：ＷＦＯ−７００）
乾燥条件：１５０℃×３０分
発泡性ポリスチレン系樹脂粒子の重量Ｗ１（ｇ）を測定し、１５０℃の乾燥機に３０分静置して、再度重量Ｗ２（ｇ）を測定する。この乾燥前後の重量差（Ｗ１−Ｗ２）が発泡性ポリスチレン系樹脂粒子内の揮発分量である。
揮発分は、下記の式により、算出する。
(Measurement of volatile matter)
Dryer: Blower constant temperature dryer (manufactured by Tokyo Rika Kikai Co., Ltd .: WFO-700)
Drying conditions: 150 ° C. × 30 minutes The weight W1 (g) of the effervescent polystyrene resin particles is measured, allowed to stand in a dryer at 150 ° C. for 30 minutes, and the weight W2 (g) is measured again. The weight difference (W1-W2) before and after drying is the amount of volatile matter in the foamable polystyrene resin particles.
The volatile content is calculated by the following formula.
揮発分（ｗｔ％）＝（Ｗ１−Ｗ２）／Ｗ１。 Volatile content (wt%) = (W1-W2) / W1.
（表面性評価）
発泡性ポリスチレン系樹脂粒子を予備発泡機（大開工業社製：ＢＨＰ−３００）で０．０８ＭＰａの水蒸気により加熱し、嵩倍率が５０ｍｌ／ｇの予備発泡粒を得る。次に、この予備発泡粒を室温で1日養生させた後、ダイセン工業社製のＫＲ−５７成形機にて平板状発泡体を成形した。
(Surface evaluation)
The effervescent polystyrene-based resin particles are heated by a pre-foaming machine (manufactured by Daikai Kogyo Co., Ltd .: BHP-300) with steam of 0.08 MPa to obtain pre-foamed particles having a bulk ratio of 50 ml / g. Next, the pre-foamed grains were cured at room temperature for one day, and then a flat foam was molded by a KR-57 molding machine manufactured by Daisen Kogyo Co., Ltd.
得られた熱可塑性樹脂発泡体の表面状態を目視観察し、以下の基準にて表面性を評価した。
◎：表面の溶融、粒間が無く、非常に美麗。
○：表面の溶融、粒間が少なく、美麗。
△：表面の溶融、粒間があり、外観やや不良。
×：表面の溶融、粒間が多く、外観不良。
The surface condition of the obtained thermoplastic resin foam was visually observed, and the surface condition was evaluated according to the following criteria.
◎: Very beautiful with no melting of the surface and no intergrains.
◯: The surface is melted and there are few intergrains, and it is beautiful.
Δ: The surface is melted and there are intergrains, and the appearance is slightly poor.
X: Surface melts, there are many grains, and the appearance is poor.
（落球衝撃高さ測定）
ＪＩＳ Ｋ７２１１に準拠して以下の通り落球衝撃高さを測定する。
５０倍の発泡成形体を温度３５℃で１日間乾燥した後、この発泡成形体から４０ｍｍ×２００ｍｍ×２０ｍｍ（厚さ）の試験片を切り出し、恒温恒湿（２５℃×５０％）の部屋に一晩以上放置する。
(Measurement of falling ball impact height)
The falling ball impact height is measured as follows in accordance with JIS K7211.
After drying a 50-fold foam molded product at a temperature of 35 ° C. for 1 day, a test piece of 40 mm × 200 mm × 20 mm (thickness) was cut out from this foamed molded product and placed in a room at a constant temperature and humidity (25 ° C. × 50%). Leave overnight or longer.
次いで、支点間の間隔が１５０ｍｍになるように試験片の両端をクランプで固定し、重さ３２１ｇ（４２．８ｍｍφ）の剛球を所定の高さから試験片の中央部に落下させて、試験片の破壊の有無を観察する。 試験片５個が全数破壊する最低の高さから全数破壊しない最高の高さまで５ｃｍ間隔で剛球の落下高さ（試験高さ）を変えて試験して、落球衝撃高さ（ｃｍ）、すなわち５０％破壊高さを次の計算式により算出する。 Next, both ends of the test piece are clamped so that the distance between the fulcrums is 150 mm, and a hard ball weighing 321 g (42.8 mmφ) is dropped from a predetermined height to the center of the test piece to make the test piece. Observe the presence or absence of destruction. From the lowest height at which all five test pieces are destroyed to the highest height at which all five test pieces are not destroyed, the falling height (test height) of the hard ball is changed at 5 cm intervals, and the falling ball impact height (cm), that is, 50 % The fracture height is calculated by the following formula.
Ｈ５０＝Ｈｉ＋ｄ[Σ（ｉ・ｎｉ）／Ｎ±０．５]
式中の記号は次のことを意味する。
Ｈ５０：５０％破壊高さ（ｃｍ）
Ｈｉ：高さ水準（ｉ）が０のときの試験高さ（ｃｍ）であり、試験片が破壊することが予測される高さ
ｄ：試験高さを上下させるときの高さ間隔（ｃｍ）
ｉ：Ｈｉのときを０とし，１つずつ増減する高さ水準（ｉ＝…−３、−２、−１、０、１、２、３…）
ｎｉ：各水準において破壊した（又は破壊しなかった）試験片の数で、いずれか多いほうのデータを使用。尚、同数の場合はどちらを使用してもよい。
Ｎ：破壊した（又は破壊しなかった）試験片の総数（Ｎ＝Σｎｉ）で、いずれか多いほうのデータを使用。尚、同数の場合はどちらを使用してもよい。
±０．５：破壊したデータを使用するときは負の数、破壊しなかったデータを使用するときは正の数を採用する。
○：落球衝撃高さが１４ｃｍ以上
×：落球衝撃高さが１４ｃｍ未満
H50 = Hi + d [Σ (i · ni) / N ± 0.5]
The symbols in the formula mean the following.
H50: 50% destruction height (cm)
Hi: The test height (cm) when the height level (i) is 0, and the height at which the test piece is predicted to break d: The height interval (cm) when raising or lowering the test height.
i: The height level is 0 when Hi, and increases or decreases by one (i = ... -3, -2, -1, 0, 1, 2, 3 ...)
ni: The number of test pieces destroyed (or not destroyed) at each level, whichever is greater. If the numbers are the same, either one may be used.
N: The total number of test pieces destroyed (or not destroyed) (N = Σni), whichever is greater. If the numbers are the same, either one may be used.
± 0.5: Use a negative number when using corrupted data and a positive number when using unbroken data.
◯: Falling impact height is 14 cm or more
X: Falling impact height is less than 14 cm
（コーナーパッド落下衝撃試験）
試験片：１２０ｍｍ×１２０ｍｍ×１２０ｍｍ、厚み５０ｍｍ（箱の四隅部（コーナー）の形状）
保管条件：２５度×５０％１の環境下に５時間以上放置
測定方法：成形体外側（落下の際の衝突面）にダンボールをかぶせた状態で、３ｋｇの錘を加え、６９ｃｍの高さから落下させ衝撃を与え、成形体の割れ率を測定する。
○：割れ率が２０％以下
×：割れ率が２０％を超える
(Corner pad drop impact test)
Specimen: 120 mm x 120 mm x 120 mm, thickness 50 mm (shape of the four corners of the box)
Storage conditions: Leave in an environment of 25 degrees x 50% 1 for 5 hours or more Measurement method: With a cardboard covered on the outside of the molded body (collision surface when falling), add a 3 kg weight and start from a height of 69 cm. Drop it and give it an impact, and measure the cracking rate of the molded product.
◯: Cracking rate is 20% or less ×: Cracking rate exceeds 20%
（実施例１）
基材樹脂として、生産後１８０日以上経過した発泡性ポリスチレン系樹脂粒子（カネパールＨＳ：株式会社カネカ製。揮発分４．７重量％含有。）を用いた。
(Example 1)
As the base resin, effervescent polystyrene-based resin particles (Kaneka HS: manufactured by Kaneka Corporation, containing 4.7% by weight of volatile matter) that had passed 180 days or more after production were used.
先ず、撹拌機つき６Ｌオートクレーブに純水９２重量部、発泡性ポリスチレン系樹脂粒子１００重量部、分散剤として第三リン酸カルシウム０．７重量部とα−オレフィンスルフォン酸ナトリウム０．０１５重量部を投入し、撹拌をスタートした後、発泡を抑制するため窒素により密閉容器内を加圧した。 First, 92 parts by weight of pure water, 100 parts by weight of foamable polystyrene resin particles, 0.7 parts by weight of calcium tertiary phosphate and 0.015 parts by weight of sodium α-olefin sulfonate were put into a 6 L autoclave with a stirrer. After starting stirring, the inside of the closed container was pressurized with nitrogen to suppress foaming.
次に、オートクレーブを１１３℃まで昇温した後、添加温度１１３℃でイソペンタン／ノルマルペンタン＝６０／４０の比率のものを２．８重量部を窒素で圧入した。その後、含浸温度を１１３℃とし６０分間保持し、その後６０分で４０℃迄冷却した。冷却終了後オートクレーブから取出し、脱水、及び、乾燥して発泡性ポリスチレン系樹脂粒子を得た。 Next, after raising the temperature of the autoclave to 113 ° C., 2.8 parts by weight of an autoclave having a ratio of isopentane / normal pentane = 60/40 was press-fitted with nitrogen at an addition temperature of 113 ° C. Then, the impregnation temperature was set to 113 ° C. and held for 60 minutes, and then cooled to 40 ° C. in 60 minutes. After the cooling was completed, the particles were taken out from the autoclave, dehydrated and dried to obtain effervescent polystyrene resin particles.
得られた発泡性ポリスチレン系樹脂粒子を篩分けして、粒子径０．６ｍｍ〜１．２ｍｍを分取した。 分取した発泡性熱可塑性樹脂粒子を、予備発泡機［大開工業製、ＢＨＰ−３００］を用いて、吹き込み蒸気圧０．０８ＭＰａの条件にて嵩倍率５０倍に予備発泡を実施した。その後、常温下で１日放置して、養生乾燥を行った。 The obtained foamable polystyrene-based resin particles were sieved and the particle diameters of 0.6 mm to 1.2 mm were separated. The separated foamable thermoplastic resin particles were pre-foamed using a pre-foaming machine [manufactured by Daikai Kogyo Co., Ltd., BHP-300] at a bulk ratio of 50 times under the condition of a blowing vapor pressure of 0.08 MPa. Then, it was left at room temperature for one day to cure and dry.
得られたスチレン系樹脂予備発泡粒子を、成形機[ダイセン製、ＫＲ−５７]を用いて、平板形状の金型内に充填し、型内成形を行い、発泡成形体を得た。 The obtained styrene-based resin pre-foamed particles were filled in a flat plate-shaped mold using a molding machine [manufactured by Daisen, KR-57] and molded in the mold to obtain a foamed molded product.
成形体強度は、落球衝撃高さが１８ｃｍ、コーナーパッド割れ率が２％であり、いずれも合格であった。結果を表１に示す。 As for the strength of the molded body, the impact height of the falling ball was 18 cm and the cracking rate of the corner pad was 2%, both of which were acceptable. The results are shown in Table 1.
（実施例２〜９、比較例１〜４）
表１に記載のとおり、基材樹脂（ブタジエンを含有しないものはカネパールＮＳＧ：株式会社カネカ製を使用）、発泡剤組成、発泡剤量、添加温度、含浸温度を変更した以外は、実施例１と同様の方法で発泡性ポリスチレン系樹脂粒子、予備発泡粒子、発泡成形体を得て、同様の評価を実施した。尚、添加した発泡剤の圧力若しくは不揮発性の気体の圧力により、発泡剤添加前に発泡性ポリスチレン系樹脂粒子が密閉容器内で発泡することを抑制した。
(Examples 2 to 9, Comparative Examples 1 to 4)
As shown in Table 1, Example 1 except that the base resin (the one containing no butadiene is Kaneka NSG: manufactured by Kaneka Corporation), the foaming agent composition, the foaming agent amount, the addition temperature, and the impregnation temperature were changed. Foamable polystyrene resin particles, pre-foamed particles, and foamed molded product were obtained in the same manner as in the above, and the same evaluation was carried out. The pressure of the added foaming agent or the pressure of the non-volatile gas suppressed the foaming polystyrene-based resin particles from foaming in the closed container before the addition of the foaming agent.
Claims (7)
添加する発泡剤が、少なくともノルマルペンタン及びイソペンタンを含む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。 Foamable polystyrene resin particles made of a resin obtained by copolymerizing a styrene monomer and butadiene, and having a volatile content of 0.1% by weight or more when dried at 150 ° C. for 30 minutes after 40 days or more have passed since production. When the amount of the foamable polystyrene resin particles is 100 parts by weight, the foaming agent is added by 0.1 part by weight or more and 7.4 parts by weight or less with respect to the foamable polystyrene resin particles of 6.5% by weight or less. It has a step of reducing the volatile content volatilized when dried at 150 ° C. for 30 minutes to 6.6% by weight or more and 8.0% by weight or less .
A method for producing foamable polystyrene-based resin particles, wherein the foaming agent to be added contains at least normal pentane and isopentane .
添加する発泡剤の添加温度が９５℃以上１１５℃以下あ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。A method for producing effervescent polystyrene-based resin particles, wherein the addition temperature of the foaming agent to be added is 95 ° C. or higher and 115 ° C. or lower.
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