JP2007169408A - Styrenic resin expandable particle, method for producing the same and in-mold expansion molded product - Google Patents
Styrenic resin expandable particle, method for producing the same and in-mold expansion molded product Download PDFInfo
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本発明は、スチレン系樹脂回収品を用いた難燃性発泡性粒子とその製造方法、またその発泡性粒子を型内発泡成形して得られた型内発泡成形体に関する。 The present invention relates to flame-retardant foamable particles using a styrene-based resin recovered product, a method for producing the same, and an in-mold foam-molded product obtained by in-mold foam-molding the foamable particles.
スチレン系樹脂発泡成形品の回収ペレットや廃家電より分別回収されたスチレン系樹脂等の使用済みのスチレン系樹脂回収品を材料としてスチレン系樹脂発泡性粒子を生産することは既に実施され、その発泡成形品は、緩衝包装材等の用途に用いられている。更には使用済みのスチレン系樹脂を材料として生産される発泡性樹脂粒子発泡成形品においても、難燃性付与の要望があり、その製法や発泡性樹脂粒子に関しての提案が種々なされている（例えば、特許文献１〜４参照。）。
一般に、使用済みのスチレン系樹脂回収品を材料として得られる発泡成形品は、未使用のスチレン系樹脂を使用して得られた発泡成形品に比較し、機械的強度が劣る。それをカバーするため、使用済みスチレン系樹脂回収品中のブタジエン含有量を調整する方法は有効である。
Production of styrene resin foamable particles has already been carried out using recovered styrene resin recovered products such as styrene resin foam molded product recovered pellets and styrene resin separated and collected from waste home appliances. Molded products are used for applications such as cushioning packaging materials. Furthermore, there is also a demand for imparting flame retardancy in foamed resin particle foam molded products that are produced using used styrene resin as a material, and various proposals regarding the production method and foamable resin particles have been made (for example, , See Patent Documents 1 to 4.)
In general, a foam molded product obtained using a used styrene-based resin recovered product as a material is inferior in mechanical strength to a foam molded product obtained using an unused styrene-based resin. In order to cover it, a method of adjusting the butadiene content in the used styrene resin recovered product is effective.
特許文献１には、発泡性スチレン系樹脂発泡体を熱収縮させて比重０．４以上の熱収縮塊とし、得られる熱収縮塊を粉砕して粉砕樹脂粒子とし、次いで該粉砕樹脂粒子を分散媒に分散させ、１２０℃以下の温度で易揮発性炭化水素及び難燃性付与剤を含浸させることを特徴とする再生不定形難燃性発泡性スチレン系樹脂粒子の製造法が開示されている。 In Patent Document 1, a foamable styrene resin foam is heat-shrinked into a heat-shrinkable mass having a specific gravity of 0.4 or more, and the resulting heat-shrinkable mass is pulverized into pulverized resin particles, and then the pulverized resin particles are dispersed. Disclosed is a method for producing regenerated amorphous flame retardant expandable styrene resin particles, which is dispersed in a medium and impregnated with a readily volatile hydrocarbon and a flame retardant imparting agent at a temperature of 120 ° C. or lower. .
特許文献２には、回収されたスチレン系樹脂に含まれているブタジエン含有量を測定し、ブタジエン含有量が樹脂全体中に１〜６質量％含まれているように調整して、これを有効目開きが１．１ｍｍ以下の金網が付設された押出機に入れ、押出機内で発泡剤を含ませ、押し出すと同時に冷却して発泡を押さえ、切断して粒子とするスチレン系樹脂回収品から発泡性粒子を製造する方法が開示されている。
In
特許文献３には、（ａ）廃棄プラスチック製品から回収された回収スチレン系樹脂を粉砕もしくは減容ペレット化して回収樹脂のロットを作る工程と、（ｂ）回収樹脂のロット毎に樹脂に含まれているブタジエン含有量を測定後、必要に応じて他の樹脂を混合して、全体中のブタジエン含有量を１〜１０質量％に調整する工程と、（ｃ）ブタジエン含有量を調整された樹脂組成物を押出機に供給し溶融させ、押出機途中より発泡剤を圧入し、発泡を抑制した状態で押出し、切断して発泡性粒子とする工程と、（ｄ）発泡性粒子を成形型に充填し、加熱発泡して所望の形状に成形し、発泡成形品を製造する工程とからなり、発泡成形品の緩衝特性を、樹脂中に含ませるブタジエン含有量にて調整することを特徴とするスチレン系樹脂のリサイクル方法が開示されている。 Patent Document 3 includes (a) a step of making a recovered resin lot by pulverizing or reducing the volume of recovered styrene resin recovered from a discarded plastic product, and (b) a recovered resin lot being included in the resin. A step of adjusting the butadiene content in the whole to 1 to 10% by mass by mixing other resins as necessary after measuring the butadiene content, and (c) a resin whose butadiene content is adjusted Supplying the composition to an extruder and melting it, pressing a foaming agent in the middle of the extruder, extruding in a state of suppressing foaming, cutting to form expandable particles, and (d) forming expandable particles into a mold It consists of the steps of filling, heating and foaming to form a desired shape, and producing a foam molded product, wherein the buffering characteristics of the foam molded product is adjusted by the butadiene content contained in the resin. Recycling of styrene resin Method is disclosed.
特許文献４には、スチレン系樹脂１００質量部にハロゲン系難燃剤を０．１〜６質量部及び脂肪族ビスアマイドを０．００１〜０．３質量部含有させることを特徴とする発泡性スチレン系樹脂粒子が開示されている。
しかしながら、前記特許文献１〜４に開示されている従来技術には、次のような問題がある。 However, the conventional techniques disclosed in Patent Documents 1 to 4 have the following problems.
特許文献１は、使用済みスチレン系樹脂を用いた難燃処方を提案しているが、ここではスチレン系樹脂中にブタジエン成分が含有された場合の検討は具体的に言及されていない。また、製法も分散媒に樹脂粒子を分散し、発泡剤を圧入するものであり、設備や分散剤等の費用がかかり、工程も相対的に煩雑であるために実施し難い問題がある。 Patent Document 1 proposes a flame retardant formulation using a used styrene resin, but here, no specific mention is made of a case where a butadiene component is contained in the styrene resin. In addition, the production method involves dispersing resin particles in a dispersion medium and press-fitting a foaming agent, which costs equipment and a dispersant, and has a problem that the process is relatively complicated and difficult to implement.
特許文献２は、廃家電より分別されたブタジエン成分含有スチレン系樹脂粉砕品を材料とした発泡体の製造について検討を行っているが、ここでは難燃性能の検討は言及されていない。ブタジエン成分が多いと、スチレン系樹脂の難燃性に悪影響を及ぼすため、特許文献２に記載された技術範囲の全てで、十分な難燃性を付与することは困難である。
特許文献３についても家電製品を含んだ廃棄プラスチック製品を材料とするリサイクル方法について提案しているが、ここでは発泡体の緩衝特性付与を課題としており、発泡体の難燃性付与については言及されていない。 Patent Document 3 also proposes a recycling method using waste plastic products including household electrical appliances as a material. However, here, the problem is to impart cushioning properties to the foam, and mention is given to imparting flame retardancy to the foam. Not.
特許文献４は、難燃剤をスチレン系モノマーと共に重合時に添加する、ないしはスチレン系樹脂に発泡剤を含浸させる際に難燃剤を添加する方法で難燃性を付与するものであり、設備や分散剤等の費用がかかり、工程も相対的に煩雑となる。 Patent Document 4 gives flame retardancy by adding a flame retardant together with a styrene monomer at the time of polymerization, or by adding a flame retardant when impregnating a styrene resin with a foaming agent. Etc., and the process becomes relatively complicated.
本発明は、前記事情に鑑みてなされたもので、スチレン系樹脂回収品を使用した難燃性を有するスチレン系樹脂発泡性粒子と、該スチレン系樹脂発泡性粒子を簡単に且つ低コストで製造可能な方法の提供を目的とする。 The present invention has been made in view of the above circumstances, and styrene resin expandable particles having flame retardancy using a styrene resin recovered product, and the styrene resin expandable particles are easily and inexpensively manufactured. The aim is to provide a possible method.
本発明は、前記目的を達成するために、樹脂の熱分解ガスクロマトグラフィーによって検出されるブタジエン含有量が１〜４質量％の範囲内であり、樹脂の蛍光Ｘ線分析法によって検出される臭素系難燃剤由来の臭素含有量が４〜８質量％の範囲内であり、且つ発泡剤が含有されたスチレン系樹脂からなることを特徴とするスチレン系樹脂発泡性粒子を提供する。 In order to achieve the above object, the present invention has a butadiene content detected by pyrolysis gas chromatography of a resin in the range of 1 to 4% by mass, and bromine detected by fluorescent X-ray analysis of the resin. Provided is a styrene resin expandable particle characterized in that the bromine content derived from a flame retardant is in the range of 4 to 8% by mass and is composed of a styrene resin containing a foaming agent.
本発明のスチレン系樹脂発泡性粒子において、スチレン系樹脂は、スチレン系樹脂回収品を含むことが好ましい。 In the styrene resin expandable particle of the present invention, the styrene resin preferably includes a styrene resin recovered product.
また本発明は、（ａ）スチレン系樹脂回収品を粉砕して粉砕品のロットを作るか、又はその粉砕品を押出機を通して作製したペレットのロットを作り、（ｂ）ロットごとに樹脂の熱分解ガスクロマトグラフィーによって検出されるブタジエン含有量と樹脂の蛍光Ｘ線分析法によって検出される臭素系難燃剤由来の臭素含有量を決定し、（ｃ）単一ロットのまま、又はブタジエン含有量及び臭素含有量の異なる複数のロットを用いるか、又はこれに未使用のスチレン系樹脂とブタジエン含有樹脂と臭素系難燃剤からなる群から選択される１種又は２種以上の添加成分を加えて、全体中のブタジエン含有量が１〜４質量％の範囲内となり、且つ臭素含有量が４〜８質量％の範囲内となるように原料樹脂を調整し、（ｄ）調整した原料樹脂を押出機に投入し、（ｅ）押出機内で原料樹脂を溶融し、溶融物に発泡剤を圧入し、溶融物を押出機の先端に付設したダイの小孔から押し出し、（ｆ）押し出すと同時に溶融物を切断するとともに急冷し、発泡を抑えて発泡性粒子とするか、又は押し出すと同時に溶融物を急冷して発泡を抑えてストランド状に固めた後、該ストランドを切断して発泡性粒子とすることを特徴とするスチレン系樹脂発泡性粒子の製造方法を提供する。 In the present invention, (a) a styrene-based resin recovered product is pulverized to make a pulverized product lot, or a pulverized product is made through a extruder to make a lot of pellets. Determine the butadiene content detected by cracked gas chromatography and the bromine content derived from brominated flame retardants detected by X-ray fluorescence analysis of the resin, (c) as a single lot or as butadiene content and A plurality of lots having different bromine contents are used, or one or two or more additional components selected from the group consisting of unused styrene-based resins, butadiene-containing resins, and brominated flame retardants are added thereto, The raw material resin is adjusted so that the butadiene content in the whole is in the range of 1 to 4% by mass and the bromine content is in the range of 4 to 8% by mass, and (d) the adjusted raw material resin is an extruder. (E) The raw material resin is melted in the extruder, a foaming agent is pressed into the melt, the melt is extruded from a small hole in a die attached to the tip of the extruder, and (f) the melt is simultaneously extruded. Cutting and quenching to suppress foaming into foamable particles, or simultaneously extruding and quenching the melt to suppress foaming and consolidating into strands, then cutting the strands into foamable particles The manufacturing method of the styrene resin expandable particle characterized by these is provided.
本発明のスチレン系樹脂発泡性粒子の製造方法において、スチレン系樹脂回収品が、家電製品又は事務用機器のハウジング部材として用いられたスチレン系樹脂成形体から回収された回収品であることが好ましく、特にスチレン系樹脂回収品に予めブタジエン成分と臭素系難燃剤との一方又は両方が含まれているものを選択して用いることが好ましい。もちろん、スチレン系樹脂回収品が、家電製品又は事務用機器の梱包用緩衝材として用いられたスチレン系樹脂発泡成形体から回収された回収品や、魚箱又は食品包装容器として用いられたスチレン系樹脂発泡成形体から回収された回収品、あるいは日用品として用いられた非発泡のスチレン系樹脂成形体から回収された回収品であってもよい。 In the method for producing styrene resin expandable particles of the present invention, the styrene resin recovered product is preferably a recovered product recovered from a styrene resin molded article used as a housing member of a home appliance or office equipment. In particular, it is preferable to select and use one in which one or both of a butadiene component and a brominated flame retardant are contained in advance in the styrene-based resin recovered product. Of course, styrene resin recovered products are recovered from styrene resin foam moldings used as packing materials for packaging of household electrical appliances or office equipment, and styrene resins used as fish boxes or food packaging containers. It may be a recovered product recovered from a resin foam molded body or a recovered product recovered from a non-foamed styrene resin molded body used as a daily necessities.
また本発明は、前述した本発明に係るスチレン系樹脂発泡性粒子を予備加熱発泡させて得られた予備発泡粒子を成形型のキャビティ内に充填し、型内発泡成形して得られた型内発泡成形品を提供する。
本発明の型内発泡成形品としては、建材用型内発泡成形品又は土木用型内発泡成形ブロックが挙げられる。
Further, the present invention provides a mold obtained by filling pre-expanded particles obtained by preheating and foaming the above-mentioned styrene resin expandable particles according to the present invention into a cavity of a mold, and performing in-mold foam molding. Provide foam molded products.
Examples of the in-mold foam molded product of the present invention include an in-mold foam molded product for building materials or an in-mold foam molded block for civil engineering.
本発明のスチレン系樹脂発泡性粒子は、樹脂の熱分解ガスクロマトグラフィーによって検出されるブタジエン含有量が１〜４質量％の範囲内でブタジエン成分を含み、且つ樹脂の蛍光Ｘ線分析法によって検出される臭素系難燃剤由来の臭素含有量が４〜８質量％の範囲内で臭素系難燃剤を含むものなので、曲げ強度などの機械特性に優れ、且つ十分な難燃性能を満たす型内発泡成形品を得ることができ、難燃性が要求される用途、例えば、断熱材などの建材用型内発泡成形品、又は土木用型内発泡成形ブロック、又は自動車用発泡内装材等として好適に用いることができる。
本発明のスチレン系樹脂発泡性粒子は、少なくとも一部の樹脂にスチレン系樹脂回収品を用いて製造した場合でも、未使用のスチレン系樹脂から作られたスチレン系樹脂型内発泡成形体に匹敵する曲げ強度などの機械特性を持つ型内発泡成形体を得ることができるので、スチレン系樹脂回収品のリサイクルに極めて有効であり、低コストで高品質の型内発泡成形体を提供することができる。
本発明のスチレン系樹脂発泡性粒子の製造方法によれば、スチレン系樹脂回収品を用いて、未使用のスチレン系樹脂から作られたスチレン系樹脂型内発泡成形体に匹敵する曲げ強度などの機械特性を持つ型内発泡成形体を製造可能なスチレン系樹脂発泡性粒子を効率よく製造することができるので、スチレン系樹脂回収品のリサイクルに極めて有効であり、低コストで高品質のスチレン系樹脂発泡性粒子を提供することができる。
The styrene resin expandable particles of the present invention contain a butadiene component within a range of 1 to 4% by mass of butadiene, which is detected by pyrolysis gas chromatography of the resin, and are detected by a fluorescent X-ray analysis method of the resin. In-mold foaming with excellent mechanical properties such as bending strength and sufficient flame retardant performance because it contains bromine flame retardant within the range of 4-8% by mass of bromine derived from brominated flame retardant Suitable for applications where flame retardant properties are required, for example, in-mold foam molded products for building materials such as heat insulating materials, or in-mold foam molded blocks for civil engineering, or automobile foam interior materials Can be used.
The styrene resin expandable particles of the present invention are comparable to the styrene resin in-mold foam-molded article made from an unused styrene resin even when manufactured using a styrene resin recovered product as at least a part of the resin. In-mold foam molded products with mechanical properties such as bending strength can be obtained, so it is extremely effective in recycling styrene-based resin recovered products, and it is possible to provide low-cost, high-quality in-mold foam molded products. it can.
According to the method for producing styrene resin expandable particles of the present invention, using a styrene resin recovered product, such as bending strength comparable to a styrene resin in-mold foam molded body made from an unused styrene resin. Styrenic resin foamable particles that can produce in-mold foam molded products with mechanical properties can be produced efficiently, so it is extremely effective for recycling styrene resin-recovered products. Resin expandable particles can be provided.
本発明のスチレン系樹脂発泡性粒子は、樹脂の熱分解ガスクロマトグラフィーによって検出されるブタジエン含有量が１〜４質量％の範囲内であり、樹脂の蛍光Ｘ線分析法によって検出される臭素系難燃剤由来の臭素含有量が４〜８質量％の範囲内であり、且つ発泡剤が含有されたスチレン系樹脂からなることを特徴としている。 The styrene resin expandable particles of the present invention have a butadiene content of 1 to 4% by mass detected by resin pyrolysis gas chromatography, and a bromine system detected by fluorescent X-ray analysis of the resin. The bromine content derived from a flame retardant is in the range of 4 to 8% by mass, and is made of a styrene resin containing a foaming agent.
本発明のスチレン系樹脂発泡性粒子のベース樹脂は、ブタジエン含有量が１〜４質量％の範囲内、且つ臭素含有量が４〜８質量％の範囲内で含有しているスチレン系樹脂である。本発明において、このスチレン系樹脂は、少なくとも一部にスチレン系樹脂回収品を含むことが好ましい。なお、本発明においてスチレン系樹脂とは、スチレン、メチルスチレン、ジメチルスチレン等のスチレン系ビニル単量体を主構成単位とする重合体である。また、スチレン系樹脂回収品は、廃棄プラスチック製品から回収されたスチレン系樹脂であり、元の製品により組成や性質も色々である。スチレン系樹脂は、スチレン系ビニル単量体だけからなる重合体の他、スチレン系ビニル単量体と他のビニル系単量体との共重合体であり得る。他のビニル系単量体は、アクリル酸、メタクリル酸、アクリル酸エステル、メタクリル酸エステル、アクリロニトリル、アクリルアミド、メタクリロニトリル、無水マレイン酸、ブタジエン、イソプレン、イソプレン、クロロプレン等を含むものであり得る。これら他のビニル系単量体は、スチレン系樹脂中に５０質量％以下含まれているものとする。 The base resin of the styrene resin expandable particles of the present invention is a styrene resin containing a butadiene content in the range of 1 to 4% by mass and a bromine content in the range of 4 to 8% by mass. . In the present invention, the styrene resin preferably includes a styrene resin recovered product at least partially. In the present invention, the styrene-based resin is a polymer having a styrene-based vinyl monomer such as styrene, methylstyrene, or dimethylstyrene as a main structural unit. Further, the styrene-based resin recovered product is a styrene-based resin recovered from a discarded plastic product, and has various compositions and properties depending on the original product. The styrenic resin may be a copolymer of a styrenic vinyl monomer and another vinyl monomer in addition to a polymer composed of only a styrenic vinyl monomer. Other vinyl monomers may include acrylic acid, methacrylic acid, acrylic ester, methacrylic ester, acrylonitrile, acrylamide, methacrylonitrile, maleic anhydride, butadiene, isoprene, isoprene, chloroprene and the like. These other vinyl monomers are contained in the styrene resin in an amount of 50% by mass or less.
本発明のスチレン系樹脂発泡性粒子は、樹脂の熱分解ガスクロマトグラフィーによって検出されるブタジエン含有量が１〜４質量％の範囲内となるようにブタジエン成分を含んでいる。このブタジエン成分は、スチレン−ブタジエン共重合体やアクリロニトリル−ブタジエン−スチレン共重合体などの共重合体として、又はブタジエンゴムなどとして存在し、これらがスチレン系樹脂にブレンドされた状態になっている。このブタジエン含有量が１〜４質量％の範囲内であれば、スチレン系樹脂発泡性粒子を用いて製造した型内発泡成形品の曲げ強度などの機械特性が良好となり、スチレン系樹脂回収品を主体として発泡性粒子を製造した場合でも、未使用のスチレン系樹脂から作られたスチレン系樹脂型内発泡成形体に匹敵する曲げ強度などの機械特性を持つ型内発泡成形体を得ることができる。一方、ブタジエン含有量が１質量％未満であると、スチレン系樹脂発泡性粒子を用いて製造した型内発泡成形品の曲げ強度などの機械特性が低下する場合がある。また、ブタジエン含有量が４質量％を超えると、型内発泡成形品の難燃性が低下し、臭素系難燃剤の添加による型内発泡成形品の難燃性付与効果を減耗させるために好ましくない。 The styrene resin expandable particles of the present invention contain a butadiene component so that the butadiene content detected by pyrolysis gas chromatography of the resin is in the range of 1 to 4% by mass. This butadiene component exists as a copolymer such as a styrene-butadiene copolymer or an acrylonitrile-butadiene-styrene copolymer, or as a butadiene rubber, and these are blended with a styrene resin. If the butadiene content is in the range of 1 to 4% by mass, the mechanical properties such as bending strength of the in-mold foam-molded product produced using the styrene-based resin foamable particles will be good, and the styrene-based resin recovered product will be Even when foamable particles are produced as a main component, an in-mold foam molded product having mechanical properties such as bending strength comparable to that of a styrene resin in-mold foam molded from an unused styrene resin can be obtained. . On the other hand, if the butadiene content is less than 1% by mass, mechanical properties such as bending strength of the in-mold foam-molded product produced using the styrene resin foamable particles may be deteriorated. Further, when the butadiene content exceeds 4% by mass, the flame retardancy of the in-mold foam molded product is lowered, and this is preferable in order to reduce the flame retardancy imparting effect of the in-mold foam molded product by adding a brominated flame retardant. Absent.
本発明のスチレン系樹脂発泡性粒子は、樹脂の蛍光Ｘ線分析法によって検出される臭素系難燃剤由来の臭素含有量が４〜８質量％の範囲内となるように臭素系難燃剤を含んでいる。本発明で用いる臭素系難燃剤としては、合成樹脂に添加される難燃剤として公知のものが使用できる。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臭素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−ジグリシジルエーテル等の臭素化フェノール誘導体が挙げられ、特にヘキサブロモシクロドデカン（ＨＢＣＤ）が好ましい。この臭素含有量が４質量％未満であると、スチレン系樹脂発泡性粒子を用いて製造した型内発泡成形品の難燃性能が不十分となり、例えば、ＪＩＳ Ａ ９５１１に基づく難燃性能を満たさなくなる。また、臭素含有量が８質量％を超えると、スチレン系樹脂発泡性粒子の軟化温度が低下し、押出法による発泡性粒子製造時に粒子形状が崩れ易くなり、粒子化が困難になる。
本発明のスチレン系樹脂発泡性粒子は、前記臭素系難燃剤以外の難燃剤、例えば、無機系難燃剤、リン酸エステル系難燃剤等を含んでいてもよい。
The styrene resin expandable particles of the present invention contain a brominated flame retardant so that the bromine content derived from the brominated flame retardant detected by the fluorescent X-ray analysis of the resin is in the range of 4 to 8% by mass. It is out. As the brominated flame retardant used in the present invention, known flame retardants added to synthetic resins can be used. For example, brominated aliphatic hydrocarbon compounds such as hexabromocyclododecane, tetrabromobutane and hexabromocyclohexane, brominated phenols such as tetrabromobisphenol A, tetrabromobisphenol F and 2,4,6-tribromophenol Brominated phenol derivatives such as tetrabromobisphenol A-bis (2,3-dibromopropyl ether) and tetrabromobisphenol A-diglycidyl ether, and hexabromocyclododecane (HBCD) is particularly preferable. When the bromine content is less than 4% by mass, the flame-retardant performance of the in-mold foam-molded product produced using the styrenic resin foamable particles becomes insufficient. For example, the flame-retardant performance based on JIS A 9511 is satisfied. Disappear. On the other hand, if the bromine content exceeds 8% by mass, the softening temperature of the styrenic resin expandable particles decreases, and the shape of the particles tends to collapse during the production of expandable particles by an extrusion method, making it difficult to form particles.
The styrene resin expandable particles of the present invention may contain a flame retardant other than the brominated flame retardant, for example, an inorganic flame retardant, a phosphate ester flame retardant and the like.
本発明のスチレン系樹脂発泡性粒子に添加する発泡剤としては、沸点がスチレン系樹脂の軟化点以下であって、常圧でガス状もしくは液状の有機化合物が適しており、例えば、プロパン、ｎ−ブタン、イソブタン、ｎ−ペンタン、イソペンタン、ネオペンタン、シクロペンタン、シクロペンタジエン、ｎ−ヘキサン、石油エーテル等の炭化水素、ジメチルエーテル、ジエチルエーテル、ジプロピルエーテル、メチルエチルエーテル等の低沸点のエーテル化合物、炭酸ガス、窒素等の無機ガス等が用いられる。これらの発泡剤は、一種のみを使用してもよく、また、二種以上を併用してもよい。これらのうち、好ましい発泡剤は沸点が２０〜６０℃の炭化水素であり、特に好ましくはｎ−ペンタンやイソペンタンである。また、イソペンタンとｎ−ペンタンとの混合物も好適に使用することができる。沸点が２０〜６０℃の発泡剤は、公知の発泡剤の中では比較的沸点の高いものであり、粒子化の際に水等の冷却液を常圧（１気圧）としても発泡を十分に抑制することができ、気泡のない発泡性粒子を得ることができる。また、炭化水素系の発泡剤は、スチレン系樹脂と親和性が高く、均一に吸収されやすいものであるから好ましい。 As the foaming agent to be added to the styrenic resin foamable particles of the present invention, a boiling or lower organic compound that is gaseous or liquid at normal pressure and having a boiling point equal to or lower than the softening point of the styrenic resin is suitable. -Hydrocarbons such as butane, isobutane, n-pentane, isopentane, neopentane, cyclopentane, cyclopentadiene, n-hexane, petroleum ether, low boiling point ether compounds such as dimethyl ether, diethyl ether, dipropyl ether, methyl ethyl ether, An inorganic gas such as carbon dioxide or nitrogen is used. These foaming agents may use only 1 type and may use 2 or more types together. Among these, a preferable blowing agent is a hydrocarbon having a boiling point of 20 to 60 ° C., and particularly preferably n-pentane or isopentane. Moreover, the mixture of isopentane and n-pentane can also be used conveniently. A blowing agent having a boiling point of 20 to 60 ° C. has a relatively high boiling point among known foaming agents, and sufficiently foams even when a cooling liquid such as water is used at normal pressure (1 atm) during particle formation. It is possible to obtain expandable particles that can be suppressed and have no bubbles. Hydrocarbon foaming agents are preferred because they have high affinity with styrene resins and are easily absorbed uniformly.
本発明のスチレン系樹脂発泡性粒子には、発泡性粒子を加熱発泡させた時の気泡サイズを調整するために、気泡調整剤を添加することが好ましい。この気泡調整剤としては、例えば、タルク、炭酸カルシウム、炭酸マグネシウム、珪藻土、ステアリン酸カルシウム、ステアリン酸マグネシウム、ステアリン酸バリウム、ステアリン酸アルミニウム、シリカ等が挙げられる。これらの中でも、微粉末タルクを樹脂に対して０．１〜２．０質量％添加するのが好ましい。さらに、本発明のスチレン系樹脂発泡性粒子には、前述した発泡剤や気泡調整剤以外の各種添加剤を必要に応じて添加することができる。この添加剤としては、合成樹脂製品の製造分野で用いられている公知の各種の添加剤の中から適宜選択して用いることができ、例えば、着色剤、紫外線吸収剤、酸化防止剤、可塑剤、帯電防止剤等を樹脂に添加又は粒子表面に付着させることができる。 In order to adjust the bubble size when the expandable particles are heated and foamed, it is preferable to add a cell regulator to the styrene resin expandable particles of the present invention. Examples of the air conditioner include talc, calcium carbonate, magnesium carbonate, diatomaceous earth, calcium stearate, magnesium stearate, barium stearate, aluminum stearate, silica and the like. Among these, it is preferable to add 0.1-2.0 mass% of fine powder talc with respect to resin. Furthermore, various additives other than the above-mentioned foaming agent and cell regulator can be added to the styrene resin foamable particles of the present invention as necessary. As this additive, it can be used by appropriately selecting from various known additives used in the field of manufacturing synthetic resin products. For example, a colorant, an ultraviolet absorber, an antioxidant, and a plasticizer. An antistatic agent or the like can be added to the resin or adhered to the particle surface.
本発明のスチレン系樹脂発泡性粒子の形状や粒径は、特に限定されないが、形状は球状、円柱状等が好ましく、また平均粒径は０．３〜２．０ｍｍの範囲とすることが好ましい。 The shape and particle size of the styrene resin foamable particles of the present invention are not particularly limited, but the shape is preferably spherical or cylindrical, and the average particle size is preferably in the range of 0.3 to 2.0 mm. .
本発明のスチレン系樹脂発泡性粒子は、このスチレン系樹脂発泡性粒子を予備加熱発泡させて得られた予備発泡粒子を所望形状の成形型のキャビティ内に充填し、型内発泡成形することによって、所望形状の型内発泡成形品を得ることができる。
特に、このスチレン系樹脂発泡性粒子は、樹脂の熱分解ガスクロマトグラフィーによって検出されるブタジエン含有量が１〜４質量％の範囲内でブタジエン成分を含み、且つ樹脂の蛍光Ｘ線分析法によって検出される臭素系難燃剤由来の臭素含有量が４〜８質量％の範囲内で臭素系難燃剤を含むものなので、曲げ強度などの機械特性に優れ、且つ十分な難燃性能、例えば、ＪＩＳ Ａ９５１１に基づく難燃性能を満たす型内発泡成形品を得ることができ、難燃性が要求される用途、例えば、断熱材等の建材用型内発泡成形品又は土木用型内発泡成形ブロック又は自動車用発泡内装材等として好適に用いることができる。
本発明のスチレン系樹脂発泡性粒子は、少なくとも一部の樹脂にスチレン系樹脂回収品を用いて製造した場合でも、未使用のスチレン系樹脂から作られたスチレン系樹脂型内発泡成形体に匹敵する曲げ強度などの機械特性を持つ型内発泡成形体を得ることができるので、スチレン系樹脂回収品のリサイクルに極めて有効であり、低コストで高品質の型内発泡成形体を提供することができる。
The styrene resin expandable particles of the present invention are obtained by filling pre-expanded particles obtained by preheating and foaming the styrene resin expandable particles into a cavity of a mold having a desired shape, and performing in-mold foam molding. An in-mold foam-molded product having a desired shape can be obtained.
In particular, the styrene resin expandable particles contain a butadiene component within a range of 1 to 4% by mass of butadiene, which is detected by pyrolysis gas chromatography of the resin, and is detected by fluorescent X-ray analysis of the resin. The bromine content derived from the brominated flame retardant contained in the range of 4 to 8% by mass contains the brominated flame retardant, so that it has excellent mechanical properties such as bending strength and sufficient flame retardant performance, for example, JIS A9511. In-mold foam-molded articles satisfying the flame-retardant performance based on the above, and applications that require flame retardancy, for example, in-mold foam-molded articles for building materials such as heat insulating materials, in-mold foam-molded blocks for civil engineering, or automobiles It can be suitably used as a foam interior material for use.
The styrene resin expandable particles of the present invention are comparable to the styrene resin in-mold foam-molded article made from an unused styrene resin even when manufactured using a styrene resin recovered product as at least a part of the resin. In-mold foam molded products with mechanical properties such as bending strength can be obtained, so it is extremely effective in recycling styrene-based resin recovered products, and it is possible to provide low-cost, high-quality in-mold foam molded products. it can.
次に、図面を参照して本発明のスチレン系樹脂発泡性粒子の製造方法の実施形態を説明する。なお、本実施形態は、スチレン系樹脂回収品を粉砕又はペレット化した原料樹脂を用い、この樹脂を押出機に投入し、押出機内で溶融した樹脂に発泡剤を圧入して混練後、先端のダイから押し出すと同時に溶融物を切断するとともに急冷し、発泡を抑えて発泡性粒子とする方法を例示しているが、本発明の製造方法は本例に限定されるものではない。 Next, an embodiment of a method for producing styrene resin expandable particles of the present invention will be described with reference to the drawings. In this embodiment, a raw material resin obtained by pulverizing or pelletizing a styrene-based resin recovery product is used, and this resin is put into an extruder, and after blowing a foaming agent into the melted resin in the extruder and kneading, The method of cutting out the melt simultaneously with the extrusion from the die and quenching it to suppress foaming into foamable particles is exemplified, but the production method of the present invention is not limited to this example.
図１は、本発明の製造方法に用いられる発泡性粒子製造装置を示す構成図である。この発泡性粒子製造装置は、押出機１と、押出機１の先端に取り付けられた多数の小孔を有するダイ２と、押出機１内に樹脂原料等を投入する原料供給ホッパー３と、押出機１内に装着された異物除去用のスクリーン１２と、押出機１内の溶融樹脂に発泡剤供給口５を通して発泡剤を圧入する高圧ポンプ４と、ダイ２の小孔が穿設された樹脂吐出面に冷却水を接触させるように設けられ、室内に冷却水が循環供給されるカッティング室７と、ダイ２の小孔から押し出された樹脂を切断できるようにカッティング室７内に回転可能に設けられたカッター６と、カッティング室７から冷却水の流れに同伴して運ばれる発泡性粒子を冷却水と分離すると共に脱水乾燥して発泡性粒子を得る固液分離機能付き脱水乾燥機１０と、固液分離機能付き脱水乾燥機１０にて分離された冷却水を溜める水槽８と、この水槽８内の冷却水をカッティング室７に送る高圧ポンプ９と、固液分離機能付き脱水乾燥機１０にて脱水乾燥された発泡性粒子を貯留する容器１１とを備えて構成されている。
FIG. 1 is a block diagram showing an expandable particle manufacturing apparatus used in the manufacturing method of the present invention. This expandable particle manufacturing apparatus includes an extruder 1, a
図２は、本実施形態によるスチレン系樹脂発泡性粒子の製造方法のフロー図である。
（ａ）本製造方法では、まず、分別・回収されたスチレン系樹脂回収品を粉砕又はペレット化して粉砕品のロット又はペレットのロットを作り、ロット分けする。スチレン系樹脂回収品は、予め元の製品毎に分別して回収するのが好ましい。このように予め分別しておくと、次工程でのロット毎のブタジエン含有量及び臭素含有量を決定しやすくなり、測定サンプル数を減らすことができる。またロット分けされたスチレン系樹脂回収品は、ロットごとに、よく混合しておくことが必要である。スチレン系樹脂回収品を粉砕又はペレット化する方法は、特に限定されず、処理対象となる廃棄プラスチック製品の性状、すなわち、大きさ、発泡樹脂か非発泡樹脂かの違い等に応じて適宜選択することができる。例えば、廃棄プラスチック製品が非発泡樹脂である場合には、付着しているゴミや異物を除去した後、適当な粉砕機で粉砕して粉砕品とすることができる。また廃棄プラスチック製品が家電製品の梱包用緩衝材等の発泡樹脂である場合には、適当な有機溶媒、例えばリモネン等のテルペン系有機溶媒や芳香族炭化水素等の溶媒に溶解した後、脱溶媒して樹脂塊とし、又は加熱減容化して樹脂塊とし、これを粉砕して押出機に入れ溶融混練し、押出機先端の小孔を有するダイより押し出した後にカットしてペレットとすることができる。
FIG. 2 is a flowchart of the method for producing styrene resin expandable particles according to the present embodiment.
(A) In this production method, first, the styrene-based resin recovered product that has been separated and collected is pulverized or pelletized to create a pulverized product lot or a pellet lot, and then the lots are divided. It is preferable to collect the styrene-based resin recovered product separately in advance for each original product. By separating in advance in this way, it becomes easy to determine the butadiene content and bromine content for each lot in the next step, and the number of measurement samples can be reduced. Moreover, it is necessary to mix the lots of styrene-based resin recovered products for each lot. The method for pulverizing or pelletizing the styrene-based resin recovered product is not particularly limited, and is appropriately selected according to the properties of the waste plastic product to be treated, that is, the size, the difference between the foamed resin and the non-foamed resin, and the like. be able to. For example, when the waste plastic product is a non-foamed resin, it is possible to obtain a pulverized product by removing adhering dust and foreign matter and then pulverizing with an appropriate pulverizer. Also, when the waste plastic product is a foamed resin such as a cushioning material for packaging of household electrical appliances, it is dissolved in a suitable organic solvent, for example, a terpene organic solvent such as limonene, or a solvent such as aromatic hydrocarbon, and then the solvent is removed. To make a resin lump, or heat-reduced to give a resin lump, which is pulverized, put into an extruder, melted and kneaded, extruded from a die having a small hole at the tip of the extruder, and then cut into pellets it can.
（ｂ）次に、ロット分けした粉砕品又はペレットについて、各ロットごとに樹脂の熱分解ガスクロマトグラフィーによって検出されるブタジエン含有量と樹脂の蛍光Ｘ線分析法によって検出される臭素系難燃剤由来の臭素含有量を決定する。本発明において、樹脂のブタジエン含有量及び臭素含有量は、下記のように測定して得られた値である。 (B) Next, for the pulverized product or pellet divided into lots, the butadiene content detected by resin pyrolysis gas chromatography and the brominated flame retardant detected by fluorescent X-ray analysis of the resin for each lot The bromine content of is determined. In the present invention, the butadiene content and bromine content of the resin are values obtained by measurement as follows.
＜ブタジエン含有量＞
樹脂試料をトルエンに溶解させ、メンブレンフィルターで濾過した後、ホットプレート上でフィルム化し、熱分解ガスクロマトグラフ分析法にて、樹脂の熱分解により生じる全モノマー成分中のブタジエン成分の量を定量分析し、ブタジエン含有量を測定する。分析に用いる機器、測定条件は以下の通り。
ガスクロマトグラフ装置：パーキンエルマー社製 Ａｕｔｏ Ｓｙｓｔｅｍ
キャリーポイントパイロライザー：日本分析工業社製 ＪＨＰ−３型
カラム：Ｊ＆Ｗ社製 ＤＢ−５
測定条件：
パイロホイル（５９０℃）、オーブン温度（２８０℃）、ニードル温度（３００℃）
カラム温度（５０℃（１分）→昇温１０℃/分→１００℃→昇温４０℃/分→３２０℃（３．５分））、測定時間（２０分）、キャリアーガス（ヘリウム）、キャリアー流量（１ｍｌ/分）、カラム入口圧力（１２ｐｓｉ）、注入口温度（３００℃）、検出器温度（３００℃）、試料量（５００μｇ）、スプリット比（１/４０）、定量法（絶対検量線法）
<Butadiene content>
A resin sample is dissolved in toluene, filtered through a membrane filter, and then converted into a film on a hot plate. The amount of butadiene component in the total monomer components generated by thermal decomposition of the resin is quantitatively analyzed by pyrolysis gas chromatography. The butadiene content is measured. The equipment and measurement conditions used for analysis are as follows.
Gas chromatograph: Auto System manufactured by PerkinElmer
Carry point pyrolyzer: JHP-3 type column manufactured by Nippon Analytical Industrial Co., Ltd .: DB-5 manufactured by J & W
Measurement condition:
Pyrofoil (590 ° C), oven temperature (280 ° C), needle temperature (300 ° C)
Column temperature (50 ° C. (1 minute) → temperature increase 10 ° C./min→100° C. → temperature increase 40 ° C./min→320° C. (3.5 minutes)), measurement time (20 minutes), carrier gas (helium), Carrier flow rate (1 ml / min), column inlet pressure (12 psi), inlet temperature (300 ° C.), detector temperature (300 ° C.), sample volume (500 μg), split ratio (1/40), quantitative method (absolute calibration) Line method)
＜臭素含有量＞
樹脂試料２〜３ｇを温度２００〜２３０℃にて熱プレスしてフィルムを作製する。このフィルムを５ｃｍ角に切り、質量を測定後、坪量を算出し、バランス成分をＰＳにし、臭素量を蛍光Ｘ線分析法により分析し、樹脂中の臭素含有量を算出する。分析に用いる機器、測定条件は以下の通り。
測定装置：リガク社製 蛍光Ｘ線分析装置 ＲＩＸ−２１００
測定条件：
Ｘ線管（縦型Ｒｈ／Ｃｒ管(3/2.4ＫＷ)、分析径（３０ｍｍφ）、スリット（標準）
分光結晶（ＴＡＰ（Ｆ〜Ｍｇ）ＰＥＴ（Ａｌ，Ｓｉ）Ｇｅ（Ｐ〜Ｃｌ）ＬｉＦ（Ｋ〜Ｕ））
検出器（Ｆ−ＰＣ（Ｆ〜Ｃａ）ＳＣ（Ｔｉ〜Ｕ））、測定モード（定性分析，ＦＰ薄膜法）
<Bromine content>
A resin sample 2-3g is hot-pressed at a temperature of 200-230 degreeC, and a film is produced. The film is cut into 5 cm square, and after measuring the mass, the basis weight is calculated, the balance component is PS, the bromine content is analyzed by fluorescent X-ray analysis, and the bromine content in the resin is calculated. The equipment and measurement conditions used for analysis are as follows.
Measuring device: Rigaku Corporation X-ray fluorescence analyzer RIX-2100
Measurement condition:
X-ray tube (vertical Rh / Cr tube (3 / 2.4KW), analysis diameter (30mmφ), slit (standard)
Spectral crystal (TAP (F to Mg) PET (Al, Si) Ge (P to Cl) LiF (K to U))
Detector (F-PC (F to Ca) SC (Ti to U)), measurement mode (qualitative analysis, FP thin film method)
（ｃ）次に、前述した通り、樹脂のブタジエン含有量及び臭素含有量を測定した各ロットのうち、単一ロット、又はブタジエン含有量及び臭素含有量の異なる複数のロットを用いるか、又はこれに未使用のスチレン系樹脂とブタジエン含有樹脂と臭素系難燃剤からなる群から選択される１種又は２種以上の添加成分を加えて、全体中のブタジエン含有量が１〜４質量％の範囲内となり、且つ臭素含有量が４〜８質量％の範囲内となるように樹脂原料を調整する。 (C) Next, as described above, among the lots in which the butadiene content and bromine content of the resin were measured, a single lot or a plurality of lots having different butadiene contents and bromine contents were used, or this 1 to 2 or more kinds of additive components selected from the group consisting of unused styrene resin, butadiene-containing resin and brominated flame retardant are added, and the butadiene content in the whole is in the range of 1 to 4% by mass The resin raw material is adjusted so that the bromine content is within the range of 4 to 8% by mass.
樹脂回収品は元々色々な用途に用いられたものを含んでおり、スチレン系樹脂といえども色々な種類の原料が混在している。例えば、家電製品や事務用機器のハウジング部材等に用いられている樹脂はゴム分を含んだ耐衝撃性ポリスチレン（ＨＩＰＳ）であり、一方、包装緩衝材、食品用トレー等に用いられている樹脂はブタジエン成分や臭素系難燃剤を含有しない一般ポリスチレンが多い。その他、用途に合わせて若干のスチレン以外の成分を添加し変性したものも含まれている。本発明の製造方法において、スチレン系樹脂回収品としては、家電製品又は事務用機器のハウジング部材として用いられたスチレン系樹脂発泡成形体から回収された回収品であることが好ましく、特に、スチレン系樹脂回収品に予めブタジエン成分と臭素系難燃剤との一方又は両方が含まれているものを選択して用いることが好ましい。このようなスチレン系樹脂回収品を用いることで、新たに添加するブタジエン含有樹脂や臭素系難燃剤の使用を無くし、或いはそれらの使用量を減じることができるので、原料コストの低減を図ることができる。 Resin recovered products include those originally used for various applications, and various types of raw materials are mixed even in styrene resins. For example, the resin used for housing members of home appliances and office equipment is impact resistant polystyrene (HIPS) containing rubber, while the resin used for packaging cushioning materials, food trays, etc. There are many general polystyrenes that do not contain a butadiene component or brominated flame retardant. In addition, those modified by adding some components other than styrene according to the application are also included. In the production method of the present invention, the styrene-based resin recovered product is preferably a recovered product recovered from a styrene-based resin foam molded article used as a housing member for home appliances or office equipment. It is preferable to select and use one in which one or both of a butadiene component and a brominated flame retardant are contained in the resin recovery product in advance. By using such a styrene-based resin recovered product, it is possible to eliminate the use of newly added butadiene-containing resins and brominated flame retardants, or to reduce the amount of those used, thereby reducing raw material costs. it can.
使用するロットについて、ブタジエン含有量と臭素含有量の一方又は両方が、前述したそれぞれの含有範囲を超えている場合、使用するロットにこれらの成分を含まない又はこれらの成分が少ないスチレン系樹脂回収品の別のロットを計算量混合するか、あるいは使用するロットにこれらの成分を含まない未使用のスチレン系樹脂を計算量混合し、含有範囲を超えた成分の量が適正範囲に入るようにし、不足している成分を追加することで原料樹脂の調整を行う。
一方、使用するロットについて、ブタジエン含有量と臭素含有量の一方又は両方が不足している場合には、計算量のブタジエン含有樹脂と臭素系難燃剤を添加し、各成分の量が適正範囲に入るように原料樹脂を調整する。この際、添加するブタジエン含有樹脂としては、例えば、ブタジエンゴム、スチレン−ブタジエン共重合体、アクリロニトリル−ブタジエン−スチレン共重合体などを挙げることができる。また、臭素系難燃剤としては、前述した通り、ヘキサブロモシクロドデカン（ＨＢＣＤ）等が好ましい。
When one or both of the butadiene content and bromine content exceeds the respective content ranges described above for the lot to be used, the styrene resin recovery in which these components are not included or are low in the lot used Mix another lot of the product with the calculated amount, or mix the calculated amount of unused styrenic resin that does not contain these components with the lot to be used, so that the amount of the component exceeding the content range falls within the appropriate range. The raw material resin is adjusted by adding the missing components.
On the other hand, if one or both of the butadiene content and bromine content are insufficient for the lot to be used, add the calculated amount of butadiene-containing resin and brominated flame retardant, and the amount of each component is within the appropriate range. Adjust the raw resin to enter. In this case, examples of the butadiene-containing resin to be added include butadiene rubber, styrene-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, and the like. As the brominated flame retardant, hexabromocyclododecane (HBCD) or the like is preferable as described above.
（ｄ）次に、調整した原料樹脂を、図１に示す発泡性粒子製造装置の原料供給ホッパー３から押出機１内に投入する。調整した樹脂粉砕品は、事前に良く混合してから１つの原料供給ホッパーから投入してもよいし、あるいは例えば複数のロットを用いる場合は各ロットごとに供給量を調整した複数の原料供給ホッパーから投入し、押出機内でそれらを混合してもよい。スチレン系樹脂回収品のロットは、事前に良く混合し、磁気選別や篩分け、比重選別、送風選別などの適当な選別手段により異物を除去しておくことが好ましい。 (D) Next, the adjusted raw material resin is put into the extruder 1 from the raw material supply hopper 3 of the expandable particle manufacturing apparatus shown in FIG. The adjusted resin pulverized product may be mixed well in advance and then charged from one raw material supply hopper, or, for example, when using a plurality of lots, a plurality of raw material supply hoppers whose supply amount is adjusted for each lot. And may be mixed in an extruder. It is preferable that the lot of the styrene-based resin recovered product is mixed well in advance, and foreign matters are removed by appropriate sorting means such as magnetic sorting, sieving, specific gravity sorting, and air blowing sorting.
（ｅ）押出機１内に原料樹脂を供給後、原料樹脂を加熱溶融し、発泡剤供給口５から高圧ポンプ４によって発泡剤を圧入し、溶融物に発泡剤を混合し、異物除去用のスクリーン１２を通して溶融物をさらに混練しながら先端側に移動させ、発泡剤を添加した溶融物を押出機１の先端に付設したダイ２の小孔から押し出す。
(E) After supplying the raw material resin into the extruder 1, the raw material resin is heated and melted, the blowing agent is press-fitted from the blowing agent supply port 5 by the high-pressure pump 4, the blowing agent is mixed into the melt, and foreign matter removal The melt is further moved to the front end side through the
（ｆ）ダイ２の小孔が穿設された樹脂吐出面は、室内に冷却水が循環供給されるカッティング室７内に配置され、且つカッティング室７内には、ダイ２の小孔から押し出された樹脂を切断できるようにカッター６が回転可能に設けられている。発泡剤添加済みの溶融物を押出機１の先端に付設したダイ２の小孔から押し出すと、溶融物は粒状に切断され、同時に冷却水と接触して急冷され、発泡が抑えられたまま固化してスチレン系樹脂発泡性粒子となる。
(F) The resin discharge surface in which the small hole of the
形成されたスチレン系樹脂発泡性粒子は、カッティング室７から冷却水の流れに同伴して固液分離機能付き脱水乾燥機１０に運ばれ、ここでスチレン系樹脂発泡性粒子を冷却水と分離すると共に脱水乾燥する。乾燥されたスチレン系樹脂発泡性粒子は、容器１１に貯留される。
The formed styrenic resin foamable particles are transferred from the cutting chamber 7 to the flow of cooling water and carried to the dehydrating
このスチレン系樹脂発泡性粒子の製造方法によれば、スチレン系樹脂回収品を用いて、未使用のスチレン系樹脂から作られたスチレン系樹脂型内発泡成形体に匹敵する機械特性を持つ型内発泡成形体を製造可能なスチレン系樹脂発泡性粒子を効率よく製造することができるので、スチレン系樹脂回収品のリサイクルに極めて有効であり、低コストで高品質のスチレン系樹脂発泡性粒子を提供することができる。 According to this method for producing expandable styrenic resin particles, a styrenic resin recovered product is used to produce an in-mold with mechanical properties comparable to an in-mold foam molded product made from unused styrenic resin. Styrenic resin foamable particles that can produce foamed molded products can be efficiently produced, so it is extremely effective in recycling styrene resin-recovered products and provides high-quality styrene resin foamable particles at low cost. can do.
本実施形態により得られたスチレン系樹脂発泡性粒子は、このスチレン系樹脂発泡性粒子を予備加熱発泡させて得られた予備発泡粒子を所望形状の成形型のキャビティ内に充填し、型内発泡成形することによって、所望形状の型内発泡成形品を得ることができる。 The styrenic resin foamable particles obtained according to the present embodiment are filled with the prefoamed particles obtained by preheating and foaming the styrenic resin foamable particles in a cavity of a mold having a desired shape. By molding, an in-mold foam molded product having a desired shape can be obtained.
なお、前述した実施形態では、押出機内で溶融した樹脂に発泡剤を圧入して混練後、先端のダイから押し出すと同時に溶融物を切断するとともに急冷し、発泡を抑えて発泡性粒子とする方法を用いているが、これに限らず、押し出すと同時に溶融物を急冷して発泡を抑えてストランド状に固めた後、該ストランドを切断して発泡性粒子とする方法などを用い、スチレン系樹脂発泡性粒子を製造することもできる。 In the above-described embodiment, after the foaming agent is pressed into the melted resin in the extruder and kneaded, it is extruded from the die at the tip, and at the same time, the melt is cut and rapidly cooled to suppress foaming to obtain expandable particles. However, the present invention is not limited to this, and the styrenic resin is used by a method of extruding and quenching the melt at the same time to suppress foaming and solidifying it into a strand shape, and then cutting the strand into foamable particles. Expandable particles can also be produced.
以下の実施例１〜３、比較例１〜５に記した通り、各種のスチレン系樹脂材料を用いてスチレン系樹脂発泡性粒子を製造し、それぞれのスチレン系樹脂発泡性粒子を用いて型内発泡成形品を製造し、燃焼試験によってその燃焼性を調べるとともに、曲げ強度を調べ、比較した。型内発泡成形品の発泡倍数、燃焼試験及び曲げ強度は、以下の条件で測定した。 As described in Examples 1 to 3 and Comparative Examples 1 to 5 below, various styrene resin materials are used to produce styrene resin foamable particles, and the respective styrene resin foamable particles are used in the mold. Foam molded products were manufactured, their flammability was examined by a combustion test, and bending strength was examined and compared. The expansion ratio, the combustion test, and the bending strength of the in-mold foam-molded product were measured under the following conditions.
＜発泡成形品の発泡倍数＞
発泡倍数は、試験片（例５０×５０×２５ｍｍ）の寸法と質量を有効数字３桁以上になるように測定し、次式により算出した。
発泡倍数（倍）＝試験片体積（ｃｍ３）／試験片質量（ｇ）×樹脂比重（ＰＳ：１．０５）
<Foam multiple of foam molded products>
The expansion ratio was calculated by measuring the dimension and mass of a test piece (eg 50 × 50 × 25 mm) so that it was 3 or more significant digits, and was calculated by the following formula.
Foaming multiple (times) = test piece volume (cm 3 ) / test piece mass (g) × resin specific gravity (PS: 1.05)
＜燃焼試験＞
ＪＩＳ Ａ ９５１１：１９９５「発泡プラスチック保温材」測定方法Ａ記載の方法で測定した。
測定方法：
試験片は、試料から厚さ１０ｍｍ長さ２００ｍｍ幅２５ｍｍを５個切り出し、規定の着火限界指示線及び燃焼限界指示線を付ける。試験片を火源用ろうそくで着火限界指示線まで燃焼させた後、炎を後退させ、その瞬間から炎が消えるまでの時間［消炎時間］（秒）を測定する。
火源用ろうそくは、定常燃焼時、しんの長さ約１０ｍｍの時炎の長さ５０ｍｍ以上太さ約７ｍｍ以上となるものを用いる。消炎時間３秒以内を合格とする。
<Combustion test>
It was measured by the method described in JIS A 9511: 1995 “Foamed plastic heat insulating material” measuring method A.
Measuring method:
Five test pieces are cut out from a sample, each having a thickness of 10 mm, a length of 200 mm, and a width of 25 mm. After the test piece is burned to the ignition limit indicator line with a candle for a fire source, the flame is retreated, and the time from the moment until the flame disappears [flame extinguishing time] (seconds) is measured.
As the candle for the fire source, a flame having a flame length of 50 mm or more and a thickness of about 7 mm or more is used when the length of the shin is about 10 mm during steady combustion. A flame extinguishing time of 3 seconds or less is acceptable.
＜曲げ強度＞
最大曲げ強さはＪＩＳ Ｋ ９５１１:１９９９「発泡プラスチック保温材」記載の方法に準じて測定した。すなわち、テンシロン万能試験機ＵＣＴ−５Ｔ（オリエンテック社製）を用いて、試験体サイズは７５×３００×１５ｍｍで圧縮速度を１０ｍｍ／分、先端治具は加圧くさび１０Ｒ支持台１０Ｒで、支点間距離は２００ｍｍとして測定した。
発泡倍数４０倍の成形品を試験体として用いて曲げ強度を測定した。４０倍の成形品が得られなかった時は、４０倍近傍の発泡倍数の成形品２つを試験体として用いて曲げ強度を測定し、２点を通る直線から４０倍品の曲げ強度を算出した。
<Bending strength>
The maximum bending strength was measured according to the method described in JIS K 9511: 1999 “Foamed plastic heat insulating material”. That is, using a Tensilon universal testing machine UCT-5T (Orientec Co., Ltd.), the specimen size is 75 x 300 x 15 mm, the compression speed is 10 mm / min, the tip jig is a pressure wedge 10R support base 10R, and the fulcrum The distance was measured as 200 mm.
Bending strength was measured using a molded article having a foaming ratio of 40 times as a test specimen. When a 40-fold molded product could not be obtained, the bending strength was measured using two molded products with an expansion ratio of about 40 times as a specimen, and the bending strength of the 40-fold product was calculated from a straight line passing through two points. did.
［実施例１］
廃棄テレビ製品のハウジング部材を分別回収した臭素系難燃剤を含むスチレン系樹脂粉砕品ロット（臭素含有量：６．５質量％、ブタジエン含有量：５．５質量％であった）と家電製品の梱包用緩衝材として用いられていた発泡成形体を回収してペレット化したブタジエン成分及び難燃剤を含まないスチレン系樹脂ペレットのロット（臭素含有量：０質量％、ブタジエン含有量：０質量％であった）とを５０：５０の質量比で混合し、混合原料樹脂を得た。更にこの混合原料樹脂１００質量部に対し３質量部の臭素系難燃剤ヘキサブロモシクロドデカン（以下、ＨＢＣＤと記す。）及び０．２質量部の微粉末タルクを添加し調整し、これら原料樹脂を最高温度２１０℃に設定した口径９０ｍｍ単軸押出機に投入した。押出機内で原料樹脂を溶融混練し、発泡剤として樹脂に対し５．２質量部の工業用ペンタンを押出機途中より圧入した。押出機内で樹脂と発泡剤を混練するとともに冷却し、押出機先端部での樹脂温度を１５８℃、ダイの樹脂導入部の圧力を１５ＭＰａに保持し、直径０．７ｍｍの小孔が１９２個配置されたダイより、このダイに連結された３０℃の水が循環するカッティング室に発泡剤含有溶融樹脂を押出すと同時に、円周方向に１０枚の刃を有する高速回転カッターで押出し物を切断した。切断した粒子を冷却、脱水乾燥してスチレン系樹脂発泡性粒子を得た。押出しは容易であり、安定して行うことができた。
得られたスチレン系発泡性粒子について、臭素含有量及びブタジエン含有量を測定したところ、臭素含有量５．３質量％、ブタジエン含有量２．７質量％であった。
次に、得られたスチレン系樹脂発泡性粒子を７２時間熟成した後、バッチ式予備発泡機にて嵩倍数４２倍の予備発泡粒子を作製した。
次に、得られた嵩倍数４２倍の予備発泡粒子を２４時間放置後、３００ｍｍ×４００ｍｍ×５０ｍｍのキャビティを持つ成形型内に充填し、ゲージ圧０．８ｋｇ／ｃｍ２の水蒸気を２０秒吹き込んで成形し、型内発泡成形品（以下、成形品と略記する。）を得た。得られた成形品の発泡倍数は４０倍で外観及び融着は良好であった。
成形品について、ＪＩＳ Ａ ９５１１に基づく難燃性能を測定した結果、発泡倍数４０倍の成形品の試験片の消炎時間は２．１秒であり、合格３秒以下を満たした。また、曲げ強度を測定した結果、発泡倍数４０倍での値は０．２７ＭＰａとなり、後述する比較例２、即ち未使用のポリスチレン樹脂を用い同様な製法で難燃性能を施した成形品強度（０．２８ＭＰａ）と同等であった。
[Example 1]
Lot of styrene resin containing brominated flame retardant (collected bromine content: 6.5% by mass, butadiene content: 5.5% by mass) collected separately from the housing parts of waste TV products and household appliances A lot of styrene resin pellets containing no butadiene component and flame retardant recovered from pellets of foamed moldings used as packing materials for packing (bromine content: 0% by mass, butadiene content: 0% by mass) Were mixed at a mass ratio of 50:50 to obtain a mixed raw material resin. Further, 3 parts by mass of a brominated flame retardant hexabromocyclododecane (hereinafter referred to as HBCD) and 0.2 parts by mass of fine powder talc are added to 100 parts by mass of the mixed raw resin, and the raw resin is adjusted. It was put into a single-screw extruder having a diameter of 90 mm set at a maximum temperature of 210 ° C. The raw material resin was melt-kneaded in the extruder, and 5.2 parts by mass of industrial pentane was injected into the resin as a foaming agent from the middle of the extruder. The resin and foaming agent are kneaded and cooled in the extruder, the resin temperature at the extruder tip is kept at 158 ° C., the pressure at the resin introduction part of the die is kept at 15 MPa, and 192 small holes with a diameter of 0.7 mm are arranged. The extruded resin containing foaming agent is extruded into a cutting chamber connected to this die through which water at 30 ° C circulates, and the extrudate is cut with a high-speed rotary cutter having 10 blades in the circumferential direction. did. The cut particles were cooled, dehydrated and dried to obtain styrene resin foamable particles. Extrusion was easy and stable.
When the bromine content and the butadiene content were measured for the obtained styrenic expandable particles, the bromine content was 5.3 mass% and the butadiene content was 2.7 mass%.
Next, after the obtained styrene resin expandable particles were aged for 72 hours, pre-expanded particles having a bulk multiple of 42 times were prepared using a batch-type pre-expanding machine.
Next, the obtained pre-expanded particles having a bulk multiple of 42 times were allowed to stand for 24 hours, and then filled into a mold having a cavity of 300 mm × 400 mm × 50 mm, and water vapor with a gauge pressure of 0.8 kg / cm 2 was blown in for 20 seconds. To obtain an in-mold foam molded product (hereinafter abbreviated as a molded product). The obtained molded article had a foaming ratio of 40 times, and the appearance and fusion were good.
As a result of measuring the flame retardancy performance of the molded product based on JIS A 9511, the flame extinguishing time of the test piece of the molded product having a foam expansion ratio of 40 times was 2.1 seconds, which satisfied a pass of 3 seconds or less. Further, as a result of measuring the bending strength, the value at the expansion ratio of 40 times becomes 0.27 MPa, and the strength of the molded product subjected to flame retardancy performance by a similar manufacturing method using Comparative Example 2 described later, that is, an unused polystyrene resin ( 0.28 MPa).
［実施例２］
実施例１と同じ設備を用い、実施例１で用いた廃棄テレビ製品のハウジング部材を分別回収したスチレン系樹脂粉砕品ロットと家電製品梱包用緩衝材を回収したブタジエン成分及び難燃剤を含まないスチレン系樹脂ペレットのロットとを２０：８０の質量比で混合し、混合原料樹脂を得た。更にこの混合原料樹脂１００質量部に対し６質量部のＨＢＣＤ及び０．２質量部の微粉末タルクを添加し調整し、実施例１と同様な方法で、スチレン系樹脂発泡性粒子、予備発泡粒子及び成形品を得た。
スチレン系樹脂発泡性粒子の臭素含有量及びブタジエン含有量を同様に測定したところ、臭素含有量５．５質量％、ブタジエン含有量１．０質量％であった。
発泡倍数３７倍の成形品の消炎時間は１．５秒と良好であり、発泡倍数４０倍品の曲げ強度も０．２６ＭＰａと比較例２と同等であった。
[Example 2]
Styrene containing no butadiene component and flame retardant recovered from a styrene-based resin pulverized product lot collected from the waste TV product housing member used in Example 1 and a home appliance packaging cushioning material using the same equipment as in Example 1. The lot of the resin pellets was mixed at a mass ratio of 20:80 to obtain a mixed raw material resin. Further, 6 parts by mass of HBCD and 0.2 parts by mass of finely powdered talc were added to 100 parts by mass of this mixed raw material resin, and styrene resin expandable particles and pre-expanded particles were prepared in the same manner as in Example 1. And a molded product was obtained.
When the bromine content and the butadiene content of the styrene resin expandable particles were measured in the same manner, the bromine content was 5.5% by mass and the butadiene content was 1.0% by mass.
The flame extinguishing time of the molded product having a foam expansion factor of 37 times was as good as 1.5 seconds, and the bending strength of the product having a foam expansion factor of 40 times was 0.26 MPa, which was equivalent to that of Comparative Example 2.
［実施例３］
実施例１と同じ設備を用い、実施例１で用いた廃棄テレビ製品のハウジング部材を分別回収したスチレン系樹脂粉砕品ロットと家電製品梱包用緩衝材を回収したブタジエン成分及び難燃剤を含まないスチレン系樹脂ペレットのロットとを７０：３０の質量比で混合し、混合原料樹脂を得た。更にこの混合原料樹脂１００質量部に対し４質量部のＨＢＣＤ及び０．２質量部の微粉末タルクを添加し調整し、実施例１と同様な方法で、スチレン系樹脂発泡性粒子、予備発泡粒子及び成形品を得た。
スチレン系樹脂発泡性粒子の臭素含有量及びブタジエン含有量を同様に測定したところ、臭素含有量７．２質量％、ブタジエン含有量３．７質量％であった。
発泡倍数３７倍の成形品の消炎時間は２．０秒と良好であり、発泡倍数４０倍品の曲げ強度も０．２６ＭＰａと比較例２と同等であった。
[Example 3]
Styrene containing no butadiene component and flame retardant recovered from a styrene-based resin pulverized product lot collected from the waste TV product housing member used in Example 1 and a home appliance packaging cushioning material using the same equipment as in Example 1. The lot of the resin pellets was mixed at a mass ratio of 70:30 to obtain a mixed raw material resin. Further, 4 parts by mass of HBCD and 0.2 parts by mass of finely powdered talc are added to 100 parts by mass of the mixed raw resin, and the styrenic resin expandable particles and pre-expanded particles are prepared in the same manner as in Example 1. And a molded product was obtained.
When the bromine content and the butadiene content of the styrene resin expandable particles were measured in the same manner, the bromine content was 7.2% by mass and the butadiene content was 3.7% by mass.
The flame extinguishing time of the molded product having a expansion ratio of 37 times was as good as 2.0 seconds, and the bending strength of the expansion ratio of 40 times was 0.26 MPa, which was equivalent to that of Comparative Example 2.
［比較例１］
実施例１と同じ設備を用い、実施例１で用いた家電製品梱包用緩衝材を回収したブタジエン成分及び難燃剤を含まないスチレン系樹脂ペレットのロットを単独で使用し、このペレット１００質量部に対し７質量部のＨＢＣＤ及び０．２質量部の微粉末タルクを添加し、実施例１と同様な方法で、スチレン系樹脂発泡性粒子、予備発泡粒子及び成形品を得た。
スチレン系樹脂発泡性粒子の臭素含有量及びブタジエン含有量を同様に測定したところ、臭素含有量７．２質量％であり、ブタジエン成分は含まれていなかった。
発泡倍数４１倍の成形品の消炎時間は１．７秒と良好であったが、発泡倍数４０倍品の曲げ強度は０．２３ＭＰａと比較例２に比較し低い値であった。
[Comparative Example 1]
Using the same equipment as in Example 1 and using a lot of styrene resin pellets that do not contain a butadiene component and a flame retardant recovered from the home appliance packaging cushioning material used in Example 1, On the other hand, 7 parts by mass of HBCD and 0.2 parts by mass of fine powder talc were added, and styrenic resin expandable particles, pre-expanded particles and a molded product were obtained in the same manner as in Example 1.
When the bromine content and the butadiene content of the styrene resin expandable particles were measured in the same manner, the bromine content was 7.2% by mass and no butadiene component was contained.
The flame extinguishing time of the molded product having a foam expansion ratio of 41 times was as good as 1.7 seconds, but the bending strength of the product having a foam expansion ratio of 40 times was 0.23 MPa, which was lower than that of Comparative Example 2.
［比較例２］
実施例１と同じ設備を用い、回収品ではなく未使用のブタジエン成分及び難燃剤を含まないポリスチレン樹脂（臭素含有量：０質量％、ブタジエン含有量：０質量％であった）を単独で使用し、この樹脂１００質量部に対し７質量部のＨＢＣＤ及び０．２質量部の微粉末タルクを添加し、実施例１と同様な方法で、スチレン系樹脂発泡性粒子、予備発泡粒子及び成形品を得た。
スチレン系樹脂発泡性粒子の臭素含有量及びブタジエン含有量を同様に測定したところ、臭素含有量４．９質量％であり、ブタジエン成分は含まれていなかった。
発泡倍数４０倍の成形品の消炎時間は１．６秒と良好であり、発泡倍数４０倍品の曲げ強度は０．２８ＭＰａであった。
[Comparative Example 2]
Using the same equipment as in Example 1, not a recovered product, but using an unused butadiene component and a flame retardant-free polystyrene resin (bromine content: 0 mass%, butadiene content: 0 mass%) alone Then, 7 parts by mass of HBCD and 0.2 parts by mass of finely powdered talc are added to 100 parts by mass of the resin, and styrene resin expandable particles, pre-expanded particles and molded products are obtained in the same manner as in Example 1. Got.
When the bromine content and the butadiene content of the styrene resin expandable particles were measured in the same manner, the bromine content was 4.9% by mass and no butadiene component was contained.
The flame extinguishing time of the molded product having a expansion ratio of 40 times was as good as 1.6 seconds, and the bending strength of the expansion ratio of the expansion ratio 40 times was 0.28 MPa.
［比較例３］
実施例１と同じ設備を用い、実施例１で用いた廃棄テレビ製品のハウジング部材を分別回収したスチレン系樹脂粉砕品ロットを単独で使用し、この樹脂１００質量部に対し０．２質量部の微粉末タルクを添加し、実施例１と同様な方法で、スチレン系樹脂発泡性粒子、予備発泡粒子及び成形品を得た。
スチレン系樹脂発泡性粒子の臭素含有量及びブタジエン含有量を同様に測定したところ、臭素含有量６．５質量％、ブタジエン含有量５．５質量％であった。
発泡倍数４０倍品の曲げ強度は０．２６ＭＰａと、比較例２と同等であったが、発泡倍数２６倍の成形品の消炎時間は６．８秒でＪＩＳ Ａ ９５１１の合格基準に及ばなかった。
[Comparative Example 3]
Using the same equipment as in Example 1, a styrene-based resin pulverized product lot obtained by separating and collecting the housing member of the waste TV product used in Example 1 was used alone, and 0.2 parts by mass of 100 parts by mass of this resin. Fine powder talc was added, and styrene resin expandable particles, pre-expanded particles and a molded product were obtained in the same manner as in Example 1.
When the bromine content and the butadiene content of the styrene resin expandable particles were measured in the same manner, the bromine content was 6.5% by mass and the butadiene content was 5.5% by mass.
The flexural strength of the 40-fold expansion product was 0.26 MPa, which was equivalent to Comparative Example 2. However, the flame-extinguishing time of the molded product with 26-fold expansion ratio was 6.8 seconds, which did not meet the acceptance criteria of JIS A 9511. .
［比較例４］
実施例１と同じ設備を用い、実施例１で用いた廃棄テレビ製品のハウジング部材を分別回収したスチレン系樹脂粉砕品ロットを単独で使用し、この樹脂１００質量部に対し３質量部のＨＢＣＤ及び０．２質量部の微粉末タルクを添加し、実施例１と同様な方法で、スチレン系樹脂発泡性粒子を作製したが、得られた発泡性樹脂粒子の形状は著しく扁平したものしか得られなかった。
スチレン系樹脂発泡性粒子の臭素含有量及びブタジエン含有量を同様に測定したところ、臭素含有量８．５質量％、ブタジエン含有量５．５質量％であった。
発泡性樹脂粒子の扁平が激しいため、予備発泡及び成形は行わなかった。
[Comparative Example 4]
Using the same equipment as in Example 1, the styrene-based resin pulverized product lot obtained by separating and collecting the housing members of the waste TV product used in Example 1 was used alone, and 3 parts by mass of HBCD and 100 parts by mass of this resin were used. Styrene resin foamable particles were prepared in the same manner as in Example 1 by adding 0.2 parts by weight of fine powder talc. However, the foamable resin particles obtained were only extremely flat. There wasn't.
When the bromine content and the butadiene content of the styrene resin expandable particles were measured in the same manner, the bromine content was 8.5% by mass and the butadiene content was 5.5% by mass.
Preflating and molding were not performed because the flatness of the expandable resin particles was severe.
［比較例５］
実施例１と同じ設備を用い、実施例１で用いた廃棄テレビ製品のハウジング部材を分別回収したスチレン系樹脂粉砕品ロットと家電製品梱包用緩衝材を回収したブタジエン成分及び難燃剤を含まないスチレン系樹脂ペレットのロットとを５０：５０の質量比で混合し、混合原料樹脂を得た。更にこの混合原料樹脂１００質量部に対し０．２質量部の微粉末タルクのみを添加し、実施例１と同様な方法で、スチレン系樹脂発泡性粒子、予備発泡粒子及び成形品を得た。
スチレン系樹脂発泡性粒子の臭素含有量及びブタジエン含有量を同様に測定したところ、臭素含有量３．２質量％、ブタジエン含有量２．８質量％であった。
発泡倍数４０倍品の曲げ強度は０．２６ＭＰａと、比較例２と同等であったが、発泡倍数３７倍の成形品の消炎時間は３．６秒でＪＩＳ Ａ ９５１１の合格基準に及ばなかった。
これらの結果を表１にまとめて記す。
[Comparative Example 5]
Styrene containing no butadiene component and flame retardant recovered from a styrene-based resin pulverized product lot collected from the waste TV product housing member used in Example 1 and a home appliance packaging cushioning material using the same equipment as in Example 1. The lots of the resin pellets were mixed at a mass ratio of 50:50 to obtain a mixed raw material resin. Furthermore, only 0.2 parts by mass of fine powder talc was added to 100 parts by mass of the mixed raw material resin, and styrene resin expandable particles, pre-expanded particles and a molded product were obtained in the same manner as in Example 1.
When the bromine content and the butadiene content of the styrene resin expandable particles were measured in the same manner, the bromine content was 3.2% by mass and the butadiene content was 2.8% by mass.
The flexural strength of the 40-fold expansion product was 0.26 MPa, which was equivalent to Comparative Example 2. However, the flame extinguishing time of the molded product with a expansion ratio of 37-fold was 3.6 seconds and did not meet the acceptance criteria of JIS A 9511. .
These results are summarized in Table 1.
表１中、記号Ａ〜Ｃ、及び＊は、次の意味である。
Ａ：未使用のポリスチレン樹脂（ＨＲＭ−１０Ｎ、東洋スチレン製）。
Ｂ：家電製品の梱包用緩衝材として用いられていた発泡成形体を回収してペレット化したブタジエン成分及び難燃剤を含まないスチレン系樹脂ペレット。
Ｃ：廃棄テレビ製品のハウジング部材を分別回収した臭素系難燃剤を含むスチレン系樹脂粉砕品。
＊：比較例４では、発泡性粒子製造時、発泡性粒子の形状が著しく扁平になり発泡性粒子の製造が困難であり、発泡成形品の製造ができなかったため、各試験は実施できなかった。
In Table 1, symbols A to C and * have the following meanings.
A: Unused polystyrene resin (HRM-10N, manufactured by Toyo Styrene).
B: Styrenic resin pellets that do not contain a butadiene component and a flame retardant obtained by collecting and pelletizing a foamed molded product that has been used as a cushioning material for packaging home appliances.
C: Styrene-based resin pulverized product containing brominated flame retardant obtained by separating and collecting housing members of discarded TV products.
*: In Comparative Example 4, when the expandable particles were manufactured, the shape of the expandable particles was extremely flat and it was difficult to manufacture the expandable particles, and the foam molded product could not be manufactured. Therefore, each test could not be performed. .
表１に示す結果から、本発明に係る実施例１〜３は、スチレン系樹脂回収品を用いて、未使用のスチレン系樹脂から作られた成形体に匹敵する曲げ強度などの機械特性と難燃性を持った成形品を製造できることが実証された。 From the results shown in Table 1, in Examples 1 to 3 according to the present invention, mechanical properties such as bending strength and difficulty comparable to molded articles made from unused styrene resins using styrene resin recovered products. It has been demonstrated that flammable molded products can be produced.
１…押出機、２…ダイ、３…原料供給ホッパー、４…高圧ポンプ、５…発泡剤供給口、６…カッター、７…カッティング室、８…水槽、９…高圧ポンプ、１０…固液分離機能付き脱水乾燥機、１１…容器、１２…スクリーン。
DESCRIPTION OF SYMBOLS 1 ... Extruder, 2 ... Die, 3 ... Raw material supply hopper, 4 ... High pressure pump, 5 ... Foaming agent supply port, 6 ... Cutter, 7 ... Cutting chamber, 8 ... Water tank, 9 ... High pressure pump, 10 ... Solid-liquid separation Functional dehydration dryer, 11 ... container, 12 ... screen.
Claims (8)
（ｂ）ロットごとに樹脂の熱分解ガスクロマトグラフィーによって検出されるブタジエン含有量と樹脂の蛍光Ｘ線分析法によって検出される臭素系難燃剤由来の臭素含有量を決定し、
（ｃ）単一ロットのまま、又はブタジエン含有量及び臭素含有量の異なる複数のロットを用いるか、又はこれに未使用のスチレン系樹脂とブタジエン含有樹脂と臭素系難燃剤からなる群から選択される１種又は２種以上の添加成分を加えて、全体中のブタジエン含有量が１〜４質量％の範囲内となり、且つ臭素含有量が４〜８質量％の範囲内となるように原料樹脂を調整し、
（ｄ）調整した原料樹脂を押出機に投入し、
（ｅ）押出機内で原料樹脂を溶融し、溶融物に発泡剤を圧入し、溶融物を押出機の先端に付設したダイの小孔から押し出し、
（ｆ）押し出すと同時に溶融物を切断するとともに急冷し、発泡を抑えて発泡性粒子とするか、又は押し出すと同時に溶融物を急冷して発泡を抑えてストランド状に固めた後、該ストランドを切断して発泡性粒子とすることを特徴とするスチレン系樹脂発泡性粒子の製造方法。 (A) Crush the styrene-based resin recovered product to make a lot of the pulverized product, or pass the pulverized product through an extruder to make a lot of pellets made,
(B) Determine the butadiene content detected by pyrolysis gas chromatography of the resin and the bromine content derived from a brominated flame retardant detected by fluorescent X-ray analysis of the resin for each lot,
(C) A single lot is used, or a plurality of lots having different butadiene contents and bromine contents are used, or are selected from the group consisting of unused styrene-based resins, butadiene-containing resins, and brominated flame retardants. The raw material resin so that the butadiene content in the whole is in the range of 1 to 4% by mass and the bromine content is in the range of 4 to 8% by mass. Adjust
(D) The adjusted raw resin is put into an extruder,
(E) Melting the raw material resin in the extruder, press-fitting a foaming agent into the melt, and extruding the melt from a small hole in a die attached to the tip of the extruder,
(F) The melt is cut and quenched at the same time as extrusion, and foaming is suppressed to foamable particles, or at the same time as the extrusion, the melt is quenched to suppress foaming and solidified into a strand shape. A method for producing styrene resin expandable particles, characterized by cutting into expandable particles.
In-mold foaming for civil engineering obtained by filling pre-foamed particles obtained by preheating and foaming the styrenic resin foamable particles according to claim 1 or 2 into a mold cavity and foam-molding in the mold. Molding block.
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