JP2011093949A - Foamable polystyrene resin particles for production of banking member and process for production thereof, prefoamed particles for production of banking member, and banking member - Google Patents
Foamable polystyrene resin particles for production of banking member and process for production thereof, prefoamed particles for production of banking member, and banking member Download PDFInfo
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本発明は、環境適合性及び難燃性に優れた盛土用部材、その製造に用いられる盛土用部材製造用発泡性ポリスチレン系樹脂粒子とその製造方法に関する。 The present invention relates to an embankment member excellent in environmental compatibility and flame retardancy, an expandable polystyrene resin particle for embedding member production used in the production thereof, and a production method thereof.
従来より、発泡合成樹脂ブロックを用いた盛土は、軟弱地盤上や傾斜地での盛土や、庭園の築山での盛土、更には地下構造物の埋込み、埋戻し等に広く用いられている。このような部材に用いられる発泡体としては、強度・耐水性等の観点からポリスチレン系樹脂発泡体が多く使用されており、中でも発泡性ポリスチレン系樹脂粒子（ビーズ等とも称される）を加熱して予備発泡し、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、型内で加熱発泡、成形する型内発泡成形法で製造された発泡成形体が一般的である。 Conventionally, embankment using a foamed synthetic resin block has been widely used for embankment on soft ground or sloped land, embankment in mountain building of a garden, and embedding and backfilling of underground structures. As a foam used for such a member, a polystyrene resin foam is often used from the viewpoint of strength, water resistance, etc. Among them, an expandable polystyrene resin particle (also referred to as a bead) is heated. In general, a foam molded body manufactured by an in-mold foam molding method in which pre-foamed particles are obtained, and the obtained pre-foamed particles are filled in a cavity of a molding die, and heated and foamed and molded in the die, is generally used.
盛土用部材は、火災等の発生防止、延焼による地盤不安定化防止等の観点から、通常、一定レベル以上の難燃性能が要求されている。ポリスチレン系樹脂発泡成形体に十分な難燃性能を付与するために、発泡成形体製造用の発泡性ポリスチレン系樹脂粒子に難燃剤を添加して使用している。
従来、ポリスチレン系樹脂発泡成形体に難燃剤を添加する方法としては、難燃剤をスチレン系モノマーと共に重合時に添加する方法（例えば、特許文献１参照。）、ポリスチレン系樹脂粒子に発泡剤を含浸させる際に難燃剤を添加する方法（例えば、特許文献２〜４参照。）がある。
The embankment member is usually required to have a certain level or more of flame retardancy from the viewpoint of preventing the occurrence of a fire or the like and preventing the ground from becoming unstable due to the spread of fire. In order to impart sufficient flame retardancy to a polystyrene resin foam molded article, a flame retardant is added to the expandable polystyrene resin particles for producing the foam molded article.
Conventionally, as a method of adding a flame retardant to a polystyrene-based resin foam molded article, a method of adding a flame retardant together with a styrene monomer at the time of polymerization (for example, see Patent Document 1), polystyrene resin particles are impregnated with a foaming agent. There is a method of adding a flame retardant (for example, see
前記特許文献１〜４に開示された従来技術では、難燃剤としてヘキサブロモシクロドデカン（ＨＢＣＤ）を用いている。ヘキサブロモシクロドデカンは化学物質審査規制法第１種監視化学物質であり、経済産業省の既存化学物質安全性点検で難分解・高濃縮が指摘され、さらに欧州リスクアセス評価対象に該当するなど、その安全性には問題があることから、その使用を無くすことが望まれている。
代替の難燃剤を使用する場合、特許文献１に開示された方法では、代替の難燃剤を使用すると製造困難となる場合がある。
また、特許文献２〜４に開示されたように、ポリスチレン系樹脂粒子に発泡剤を含浸させる際、難燃剤を発泡剤と同時に加え、ポリスチレン系樹脂粒子にこれらを含浸させる方法では、粉末状難燃剤が懸濁液中で二次凝集を起こすことによって、難燃剤の懸濁液中における分散が不均一となり、その結果粉末状の難燃剤の樹脂粒子への吸収が不均一となってしまい、一部の樹脂粒子が難燃剤を多く吸収してしまうといった問題がある。
また、前記のようにポリスチレン樹脂粒子に難燃剤を含浸させて添加する方法では、ポリスチレン樹脂粒子の表面付近に難燃剤が含浸されるものの、樹脂粒子中心付近には難燃剤が存在しないか、含有量が低い樹脂粒子しか得られず、このような樹脂粒子を予備発泡し、更に得られた予備発泡粒子を型内発泡成形して得られるポリスチレン系樹脂発泡成形体は機械強度が劣り、寸法安定性が悪くなり、盛土用部材製造用途には適さなくなる。
In the prior art disclosed in Patent Documents 1 to 4, hexabromocyclododecane (HBCD) is used as a flame retardant. Hexabromocyclododecane is a type 1 monitoring chemical substance in the Chemical Substances Control Regulation Law, and it has been pointed out that it is difficult to decompose and highly concentrated in the existing chemical substance safety inspection of the Ministry of Economy, Trade and Industry, and is also subject to European risk assessment assessment. Since there is a problem with its safety, it is desired to eliminate its use.
In the case of using an alternative flame retardant, the method disclosed in Patent Document 1 may be difficult to produce if an alternative flame retardant is used.
In addition, as disclosed in
In addition, in the method of adding the polystyrene resin particles impregnated with the flame retardant as described above, the flame retardant is impregnated near the surface of the polystyrene resin particles, but the flame retardant is not present or contained near the resin particle center. Only low-resin resin particles can be obtained. Polystyrene resin foam molded products obtained by pre-foaming such resin particles and then foam-molding the obtained pre-foamed particles have poor mechanical strength and are dimensionally stable. The property becomes worse, and it is not suitable for the use for producing the material for embankment.
本発明は、前記事情に鑑みてなされ、環境や生物に対する安全性が高い難燃剤を用いて十分な難燃性能を有し、機械強度・寸法安定性にも優れた盛土用部材の提供を目的とする。 The present invention was made in view of the above circumstances, and has an object to provide a banking member having sufficient flame retardancy using a flame retardant having high safety to the environment and living organisms, and excellent in mechanical strength and dimensional stability. And
前記目的を達成するため、本発明は、難燃剤及び発泡剤を含有するポリスチレン系樹脂を粒子状としてなる盛土用部材製造用発泡性ポリスチレン系樹脂粒子であって、
前記難燃剤は、分子内に臭素原子を有し、臭素分含有量が７０質量％未満であり、分子内にベンゼン環を有し、且つ該難燃剤の５質量％分解温度が２００〜３００℃の範囲内であり、
樹脂供給装置内でポリスチレン系樹脂に難燃剤及び発泡剤を添加、混練し、難燃剤・発泡剤含有の溶融樹脂を樹脂供給装置先端に付設されたダイの小孔から直接冷却用液体中に押し出し、押し出すと同時に押出物を切断するとともに、押出物を液体との接触により冷却固化して発泡性ポリスチレン系樹脂粒子を得る溶融押出法により得られたものであることを特徴とする盛土用部材製造用発泡性ポリスチレン系樹脂粒子を提供する。
In order to achieve the above object, the present invention is an expandable polystyrene resin particle for embankment member production in which a polystyrene resin containing a flame retardant and a foaming agent is in the form of particles,
The flame retardant has a bromine atom in the molecule, a bromine content of less than 70% by mass, a benzene ring in the molecule, and a 5% by mass decomposition temperature of the flame retardant of 200 to 300 ° C. Within the range of
A flame retardant and foaming agent are added to and kneaded with polystyrene resin in the resin supply device, and the molten resin containing the flame retardant / foaming agent is extruded directly into the cooling liquid through a small hole in the die attached to the tip of the resin supply device. The material for embankment is obtained by a melt extrusion method in which extrudate is cut at the same time as extrusion and the extrudate is cooled and solidified by contact with a liquid to obtain expandable polystyrene resin particles. Expandable polystyrene resin particles for use are provided.
本発明の盛土用部材製造用発泡性ポリスチレン系樹脂粒子において、前記難燃剤が、テトラブロモビスフェノールＡまたはその誘導体からなる群から選択される１種又は２種以上であることが好ましい。 In the expandable polystyrene resin particles for embankment member production of the present invention, the flame retardant is preferably one or more selected from the group consisting of tetrabromobisphenol A or a derivative thereof.
本発明の盛土用部材製造用発泡性ポリスチレン系樹脂粒子において、前記難燃剤が、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−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（アリルエーテル）からなる群から選択される１種又は２種以上であることが好ましい。 In the foamable polystyrene resin particles for producing embankment members of the present invention, the flame retardant is tetrabromobisphenol A-bis (2,3-dibromo-2-methylpropyl ether), tetrabromobisphenol A-bis (2, 3-dibromopropyl ether) and tetrabromobisphenol A-bis (allyl ether) are preferably selected from the group consisting of one or more.
また本発明は、前記盛土用部材製造用発泡性ポリスチレン系樹脂粒子を加熱して得られた盛土用部材製造用予備発泡粒子を提供する。 The present invention also provides pre-expanded particles for producing embankment members obtained by heating the expandable polystyrene resin particles for producing embankment members.
また本発明は、前記盛土用部材製造用予備発泡粒子を成形型のキャビティ内に充填して加熱、発泡させて得られ、密度が０．０１０〜０．０５０ｇ／ｃｍ３の範囲である盛土用部材を提供する。 Further, the present invention is an embankment obtained by filling the pre-expanded particles for producing embankment members in a cavity of a mold, heating and foaming, and having a density in the range of 0.010 to 0.050 g / cm 3 . Providing a member.
また本発明は、前記盛土用部材製造用予備発泡粒子を成形型のキャビティ内に充填して加熱、発泡させて得られ、発泡倍数５０倍の発泡成形体について、気泡の平均弦長が４０〜２００μｍの範囲である盛土用部材を提供する。 Further, the present invention is obtained by filling the above-mentioned pre-expanded particles for producing embankment members into a cavity of a mold and heating and foaming. An embankment member having a range of 200 μm is provided.
また本発明は、前記盛土用部材製造用予備発泡粒子を成形型のキャビティ内に充填して加熱、発泡させて得られ、酸素指数が２６以上である盛土用部材を提供する。 The present invention also provides a banking member having an oxygen index of 26 or more obtained by filling the pre-expanded particles for manufacturing a banking member in a cavity of a mold, heating and foaming.
また本発明は、樹脂供給装置内でポリスチレン系樹脂に、分子内に臭素原子を有し、臭素分含有量が７０質量％未満であり、分子内にベンゼン環を有し、且つ該難燃剤の５質量％分解温度が２００〜３００℃の範囲内である難燃剤及び発泡剤を添加、混練し、難燃剤・発泡剤含有の溶融樹脂を樹脂供給装置先端に付設されたダイの小孔から直接冷却用液体中に押し出し、押し出すと同時に押出物を切断するとともに、押出物を液体との接触により冷却固化して、前記本発明に係る盛土用部材製造用発泡性ポリスチレン系樹脂粒子を得ることを特徴とする盛土用部材製造用発泡性ポリスチレン系樹脂粒子の製造方法を提供する。 Further, the present invention provides a polystyrene resin in a resin supply apparatus having a bromine atom in the molecule, a bromine content of less than 70% by mass, a benzene ring in the molecule, and the flame retardant. A flame retardant and a foaming agent having a 5 mass% decomposition temperature in the range of 200 to 300 ° C. are added and kneaded. Extruding into a cooling liquid, cutting the extrudate at the same time as extruding, and cooling and solidifying the extrudate by contact with the liquid to obtain expandable polystyrene resin particles for embankment production according to the present invention Provided is a method for producing expandable polystyrene resin particles for embankment member production.
本発明の盛土用部材製造用発泡性ポリスチレン系樹脂粒子の製造方法において、前記難燃剤が、テトラブロモビスフェノールＡまたはその誘導体からなる群から選択される１種又は２種以上であることが好ましい。 In the method for producing expandable polystyrene resin particles for producing embankment members according to the present invention, the flame retardant is preferably one or more selected from the group consisting of tetrabromobisphenol A or a derivative thereof.
本発明の盛土用部材製造用発泡性ポリスチレン系樹脂粒子の製造方法において、前記難燃剤が、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−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（アリルエーテル）からなる群から選択される１種又は２種以上であることが好ましい。 In the method for producing expandable polystyrene resin particles for producing a member for embankment of the present invention, the flame retardant is tetrabromobisphenol A-bis (2,3-dibromo-2-methylpropyl ether), tetrabromobisphenol A-bis. It is preferable that it is 1 type, or 2 or more types selected from the group consisting of (2,3-dibromopropyl ether) and tetrabromobisphenol A-bis (allyl ether).
本発明の盛土用部材製造用発泡性ポリスチレン系樹脂粒子の製造方法において、樹脂中に所定濃度で前記難燃剤を含むマスターバッチ材を前記ポリスチレン系樹脂とともに樹脂供給装置内に供給し、該装置内で溶融混練することが好ましい。 In the method for producing expandable polystyrene resin particles for producing embankment members according to the present invention, a master batch material containing the flame retardant at a predetermined concentration in a resin is supplied together with the polystyrene resin into a resin supply device, It is preferable to melt-knead with.
本発明の盛土用部材製造用発泡性ポリスチレン系樹脂粒子は、分子内に臭素原子を有し、臭素分含有量が７０質量％未満であり、分子内にベンゼン環を有し、且つ該難燃剤の５質量％分解温度が２００〜３００℃の範囲内である難燃剤を含有している。前記難燃剤は、環境や生物に対する安全性が高いものであり、特に、テトラブロモビスフェノールＡ誘導体は、ポリスチレン系樹脂発泡成形体に添加した場合に十分な難燃性能を付与でき、環境や生物に対する安全性が高いので、安全性に優れた盛土用部材を提供することができる。
本発明の盛土用部材製造用発泡性ポリスチレン系樹脂粒子は、樹脂供給装置内でポリスチレン系樹脂に難燃剤及び発泡剤を添加、混練し、難燃剤・発泡剤含有の溶融樹脂を樹脂供給装置先端に付設されたダイの小孔から直接冷却用液体中に押し出し、押し出すと同時に押出物を切断するとともに、押出物を液体との接触により冷却固化して発泡性ポリスチレン系樹脂粒子を得る溶融押出法により得られたものなので、樹脂粒子中に難燃剤が均一に存在しており、樹脂粒子中に難燃剤が不均一に存在しているものと比べ、得られる盛土用部材の機械強度が高くなり、成形性や寸法安定性にも優れた盛土用部材が得られる。
The expandable polystyrene resin particles for producing embankment members of the present invention have a bromine atom in the molecule, a bromine content of less than 70% by mass, a benzene ring in the molecule, and the flame retardant. It contains a flame retardant having a 5 mass% decomposition temperature of 200 to 300 ° C. The flame retardant is highly safe for the environment and organisms. In particular, the tetrabromobisphenol A derivative can impart sufficient flame retardant performance when added to a polystyrene resin foamed molded article, and is safe for the environment and organisms. Since the safety is high, it is possible to provide an embankment member that is excellent in safety.
The expandable polystyrene resin particles for embankment material production according to the present invention are prepared by adding a flame retardant and a foaming agent to a polystyrene resin in a resin supply device, kneading, and adding a flame retardant / foaming agent-containing molten resin to the tip of the resin supply device. Extruded directly from the small hole of the die attached to the cooling liquid and simultaneously extruded, cutting the extrudate, and cooling and solidifying the extrudate by contact with the liquid to obtain expandable polystyrene resin particles Since the flame retardant is uniformly present in the resin particles, the mechanical strength of the resulting embankment member is higher than that in which the flame retardant is unevenly present in the resin particles. Moreover, the embankment member excellent in moldability and dimensional stability can be obtained.
本発明の盛土用部材は、前記盛土用部材製造用発泡性ポリスチレン系樹脂粒子を加熱して予備発泡させ、更に、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て加熱、発泡させて得られたものなので、環境や生物に対する安全性が高い難燃剤を用いて十分な難燃性能を有し、機械強度・寸法安定性にも優れた盛土用部材を提供することができる。 The embankment member of the present invention heats and expands the expandable polystyrene resin particles for producing the embankment member, and further fills the obtained pre-expanded particles in a cavity of a mold and heats and expands the foamed polystyrene resin particles. Therefore, it is possible to provide an embankment member that has sufficient flame retardancy and is excellent in mechanical strength and dimensional stability by using a flame retardant having high safety to the environment and living organisms.
本発明の盛土用部材製造用発泡性ポリスチレン系樹脂粒子の製造方法によれば、前述したように優れた効果を有する盛土用部材製造用発泡性ポリスチレン系樹脂粒子を効率よく製造することができる。
また、本発明の盛土用部材製造用発泡性ポリスチレン系樹脂粒子の製造方法において、樹脂中に所定濃度で前記難燃剤を含むマスターバッチ材を前記ポリスチレン系樹脂とともに樹脂供給装置内に供給し、該装置内で溶融混練することによって、難燃剤をより均一に樹脂粒子に含有させることができる。
According to the method for producing expandable polystyrene resin particles for producing embankment members of the present invention, as described above, expandable polystyrene resin particles for producing embankment members can be efficiently produced.
In the method for producing expandable polystyrene resin particles for embankment member production of the present invention, a master batch material containing the flame retardant at a predetermined concentration in the resin is supplied together with the polystyrene resin into a resin supply device, By melt-kneading in the apparatus, the flame retardant can be more uniformly contained in the resin particles.
以下、図面を参照して本発明の実施形態を説明する。
本発明の盛土用部材製造用発泡性ポリスチレン系樹脂粒子の製造方法は、樹脂供給装置内でポリスチレン系樹脂に、分子内に臭素原子を有し、臭素分含有量が７０質量％未満であり、分子内にベンゼン環を有し、且つ該難燃剤の５質量％分解温度が２００〜３００℃の範囲内である難燃剤及び発泡剤を添加、混練し、難燃剤・発泡剤含有の溶融樹脂を樹脂供給装置先端に付設されたダイの小孔から直接冷却用液体中に押し出し、押し出すと同時に押出物を切断するとともに、押出物を液体との接触により冷却固化して盛土用部材製造用発泡性ポリスチレン系樹脂粒子を得ることを特徴としている。
Hereinafter, embodiments of the present invention will be described with reference to the drawings.
The method for producing expandable polystyrene resin particles for embankment production according to the present invention has a bromine atom in the molecule in the polystyrene resin in the resin supply apparatus, and the bromine content is less than 70% by mass, A flame retardant having a benzene ring in the molecule and a 5 mass% decomposition temperature of the flame retardant within a range of 200 to 300 ° C. and a foaming agent are added and kneaded to obtain a flame retardant / foaming agent-containing molten resin. Extruded directly into the cooling liquid through a small hole in the die attached to the tip of the resin supply device, and at the same time, extrudate is cut, and the extrudate is cooled and solidified by contact with the liquid. It is characterized by obtaining polystyrene resin particles.
図１は、本発明の盛土用部材製造用発泡性ポリスチレン系樹脂粒子の製造方法に用いられる製造装置の一例を示す構成図であり、本例の製造装置は、樹脂供給装置としての押出機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貯留容器１１とを備えて構成されている。
FIG. 1: is a block diagram which shows an example of the manufacturing apparatus used for the manufacturing method of the expandable polystyrene-type resin particle for embankment member manufacture of this invention, and the manufacturing apparatus of this example is the extruder 1 as a resin supply apparatus. A
なお、押出機１としては、スクリュを用いる押出機またはスクリュを用いない押出機のいずれも用いることができる。スクリュを用いる押出機としては、例えば、単軸式押出機、多軸式押出機、ベント式押出機、タンデム式押出機などが挙げられる。スクリュを用いない押出機としては、例えば、プランジャ式押出機、ギアポンプ式押出機などが挙げられる。また、いずれの押出機もスタティックミキサーを用いることができる。これらの押出機のうち、生産性の面からスクリュを用いた押出機が好ましい。また、カッター６を収容したカッティング室７も、樹脂の溶融押出による造粒方法において用いられている従来周知のものを用いることができる。 As the extruder 1, either an extruder using a screw or an extruder not using a screw can be used. Examples of the extruder using a screw include a single-screw extruder, a multi-screw extruder, a vent-type extruder, and a tandem extruder. Examples of the extruder that does not use a screw include a plunger type extruder and a gear pump type extruder. Moreover, any extruder can use a static mixer. Among these extruders, an extruder using a screw is preferable from the viewpoint of productivity. Moreover, the conventionally well-known thing used in the granulation method by melt extrusion of resin can also be used for the cutting chamber 7 which accommodated the cutter 6. FIG.
本発明の盛土用部材製造用発泡性ポリスチレン系樹脂粒子において、ポリスチレン系樹脂としては、特に限定されず、例えば、スチレン、α−メチルスチレン、ビニルトルエン、クロロスチレン、エチルスチレン、ｉ−プロピルスチレン、ジメチルスチレン、ブロモスチレン等のスチレン系モノマーの単独重合体又はこれらの共重合体等が挙げられ、スチレンを５０質量％以上含有するポリスチレン系樹脂が好ましく、ポリスチレンがより好ましい。 In the foamable polystyrene resin particles for producing embankment members of the present invention, the polystyrene resin is not particularly limited, and examples thereof include styrene, α-methylstyrene, vinyltoluene, chlorostyrene, ethylstyrene, i-propylstyrene, Examples include homopolymers of styrene monomers such as dimethylstyrene and bromostyrene, copolymers thereof, and the like. Polystyrene resins containing 50% by mass or more of styrene are preferable, and polystyrene is more preferable.
また、前記ポリスチレン系樹脂としては、前記スチレンモノマーを主成分とする、前記スチレン系モノマーとこのスチレン系モノマーと共重合可能なビニルモノマーとの共重合体であってもよく、このようなビニルモノマーとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、セチル（メタ）アクリレート等のアルキル（メタ）アクリレート、（メタ）アクリロニトリル、ジメチルマレエート、ジメチルフマレート、ジエチルフマレート、エチルフマレートの他、ジビニルベンゼン、アルキレングリコールジメタクリレートなどの二官能性モノマーなどが挙げられる。 Further, the polystyrene resin may be a copolymer of the styrene monomer and a vinyl monomer copolymerizable with the styrene monomer, the main component of which is the styrene monomer. As, for example, alkyl (meth) acrylate such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cetyl (meth) acrylate, (meth) acrylonitrile, dimethyl maleate, dimethyl fumarate, diethyl In addition to fumarate and ethyl fumarate, bifunctional monomers such as divinylbenzene and alkylene glycol dimethacrylate are exemplified.
また、ポリスチレン系樹脂が主成分であれば、他の樹脂を添加してもよく、添加する樹脂としては、例えば、発泡成形体の耐衝撃性を向上させるために、ポリブタジエン、スチレン−ブタジエン共重合体、エチレン−プロピレン−非共役ジエン三次元共重合体などのジエン系のゴム状重合体を添加したゴム変性ポリスチレン系樹脂、いわゆるハイインパクトポリスチレンが挙げられる。あるいは、ポリエチレン系樹脂、ポリプロピレン系樹脂、アクリル系樹脂、アクリロニトリル−スチレン共重合体、アクリロニトリル−ブタジエン−スチレン共重合体などが挙げられる。 If a polystyrene resin is the main component, other resins may be added. Examples of the resin to be added include polybutadiene, styrene-butadiene copolymer to improve the impact resistance of the foam molded article. Examples thereof include rubber-modified polystyrene resins to which a diene rubbery polymer such as a polymer, ethylene-propylene-nonconjugated diene three-dimensional copolymer is added, so-called high impact polystyrene. Alternatively, a polyethylene resin, a polypropylene resin, an acrylic resin, an acrylonitrile-styrene copolymer, an acrylonitrile-butadiene-styrene copolymer, and the like can be given.
本発明の盛土用部材製造用発泡性ポリスチレン系樹脂粒子において、原料となるポリスチレン系樹脂としては、市販されている通常のポリスチレン系樹脂、懸濁重合法などの方法で新たに作製したポリスチレン系樹脂などの、リサイクル原料でないポリスチレン系樹脂（バージンポリスチレン）を使用できる他、使用済みのポリスチレン系樹脂発泡成形体を再生処理して得られたリサイクル原料を使用することができる。このリサイクル原料としては、使用済みのポリスチレン系樹脂発泡成形体、例えば、魚箱、家電緩衝材、食品包装用トレーなどを回収し、リモネン溶解方式や加熱減容方式によって再生したリサイクル原料の中から、重量平均分子量Ｍｗが１２万〜４０万の範囲となる原料を適宜選択し、又は重量平均分子量Ｍｗが異なる複数のリサイクル原料を適宜組み合わせて用いることができる。 In the expandable polystyrene resin particles for embankment production of the present invention, the polystyrene resin as a raw material is a polystyrene resin newly produced by a method such as a commercially available ordinary polystyrene resin or suspension polymerization method. In addition to a polystyrene-based resin (virgin polystyrene) that is not a recycled material, a recycled material obtained by regenerating a used polystyrene-based resin foam molding can be used. As this recycled material, used polystyrene-based resin foam moldings such as fish boxes, household appliance cushioning materials, food packaging trays, etc. are collected and recycled from the recycled materials recovered by the limonene dissolution method or heating volume reduction method. A raw material having a weight average molecular weight Mw in the range of 120,000 to 400,000 can be appropriately selected, or a plurality of recycled raw materials having different weight average molecular weights Mw can be used in appropriate combination.
本発明の盛土用部材製造用発泡性ポリスチレン系樹脂粒子において、難燃剤としては、分子内に臭素原子を有し、臭素分含有量が７０質量％未満であり、分子内にベンゼン環を有し、且つ該難燃剤の５質量％分解温度が２００〜３００℃の範囲内である難燃剤が用いられ、前記難燃剤の１種又は２種以上を混合して、或いは、前記難燃剤を主体として、それに他の難燃剤を組み合わせて使用してもよい。
臭素分含有量が７０質量％を超え、分子内にベンゼン環を有さない難燃剤は、環境や生物に対する安全性が高い難燃剤となり難く、また機械強度・成形性・寸法安定性にも優れた盛土用部材を提供するという本発明の効果を達成し難くなる。臭素分含有量の下限は特に限定しないが５０質量％以上であれば難燃効率が良いので好ましい。臭素分含有量のより好ましい範囲は５５〜６９質量％である。
また、該難燃剤の５質量％分解温度が２００℃未満であると、難燃剤とポリスチレン系樹脂とを押出機１内で溶融混練する際に、難燃剤が分解して難燃効果が得られなくなる恐れがある。５質量％分解温度が３００℃を超える難燃剤を用いた場合には、得られる盛土用部材の難燃性が低下してしまう。該難燃剤の５質量％分解温度の好ましい範囲は２３０〜３００℃であり、より好ましい範囲は２４０〜２９５℃であり、最も好ましい範囲は２６５〜２９０℃である。
In the foamable polystyrene resin particles for producing embankment members of the present invention, the flame retardant has a bromine atom in the molecule, a bromine content of less than 70% by mass, and a benzene ring in the molecule. In addition, a flame retardant having a 5% by mass decomposition temperature of the flame retardant within a range of 200 to 300 ° C. is used, or one or more of the flame retardants are mixed, or the flame retardant is mainly used. In addition, other flame retardants may be used in combination.
A flame retardant with a bromine content of more than 70% by mass and no benzene ring in the molecule is unlikely to be a flame retardant that is highly safe for the environment and organisms, and has excellent mechanical strength, moldability, and dimensional stability. It becomes difficult to achieve the effect of the present invention that provides a member for embankment. The lower limit of the bromine content is not particularly limited, but 50% by mass or more is preferable because the flame retardancy is good. A more preferable range of bromine content is 55 to 69 mass%.
Further, when the 5 mass% decomposition temperature of the flame retardant is less than 200 ° C., when the flame retardant and polystyrene resin are melt-kneaded in the extruder 1, the flame retardant decomposes and a flame retardant effect is obtained. There is a risk of disappearing. When a flame retardant having a 5 mass% decomposition temperature exceeding 300 ° C. is used, the flame retardancy of the resulting embankment member is lowered. The preferable range of 5 mass% decomposition temperature of this flame retardant is 230-300 degreeC, The more preferable range is 240-295 degreeC, The most preferable range is 265-290 degreeC.
本発明において、好ましい難燃剤としては、テトラブロモビスフェノールＡまたはその誘導体からなる群から選択される１種又は２種以上が挙げられる。これらの難燃剤の中でも、特に、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−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（アリルエーテル）からなる群から選択される１種又は２種以上であることが好ましい。５％分解温度が高い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）がより好ましく、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）が最も好ましい。
本発明の盛土用部材製造用発泡性ポリスチレン系樹脂粒子において、前記難燃剤の添加量は、盛土用部材製造用発泡性ポリスチレン系樹脂粒子の樹脂分１００質量部に対して０．５〜８．０質量％の範囲とすることが好ましく、１．０〜６．０質量％の範囲が更に好ましい。難燃剤の添加量が前記範囲未満であると、得られる盛土用部材の難燃性が低下してしまう。難燃剤の添加量が前記範囲を超えると、得られる盛土用部材の機械強度・成形性・寸法変化率が劣化してしまう恐れがある。
In the present invention, preferred flame retardants include one or more selected from the group consisting of tetrabromobisphenol A or derivatives thereof. Among these flame retardants, tetrabromobisphenol A-bis (2,3-dibromo-2-methylpropyl ether), tetrabromobisphenol A-bis (2,3-dibromopropyl ether), tetrabromobisphenol A- It is preferable that it is 1 type, or 2 or more types selected from the group consisting of bis (allyl ether). Tetrabromobisphenol A-bis (2,3-dibromopropyl ether) and tetrabromobisphenol A-bis (2,3-dibromo-2-methylpropyl ether) having a high 5% decomposition temperature are more preferred, and tetrabromobisphenol A- Bis (2,3-dibromopropyl ether) is most preferred.
In the expandable polystyrene resin particles for producing embankment members of the present invention, the amount of the flame retardant added is 0.5 to 8.8 based on 100 parts by mass of the resin content of the expandable polystyrene resin particles for embankment member production. It is preferable to set it as the range of 0 mass%, and the range of 1.0-6.0 mass% is still more preferable. When the addition amount of the flame retardant is less than the above range, the flame retardancy of the obtained embankment member is lowered. If the amount of the flame retardant added exceeds the above range, the mechanical strength, formability, and dimensional change rate of the resulting embankment member may be deteriorated.
本発明の盛土用部材製造用発泡性ポリスチレン系樹脂粒子において、発泡剤としては特に限定されないが、例えば、ノルマルペンタン、イソペンタン、シクロペンタン、シクロペンタジエン等を単独で、もしくは２種以上混合して使用することができる。また、前記ペンタン類を主成分として、ノルマルブタン、イソブタン、プロパン等を混合して使用することもできる。特にペンタン類は、ダイの小孔から水流中に吐出される際の樹脂粒子の発泡を抑制しやすいので好適に用いられる。ポリスチレン系樹脂に含有させる前記発泡剤の量は、ポリスチレン系樹脂１００質量部に対し、３〜１０質量部の範囲であり、より好ましくは４〜７質量部の範囲である。 In the foamable polystyrene resin particles for embankment production according to the present invention, the foaming agent is not particularly limited. For example, normal pentane, isopentane, cyclopentane, cyclopentadiene, etc. are used alone or in admixture of two or more. can do. Further, normal butane, isobutane, propane and the like can be mixed and used with the pentane as a main component. In particular, pentanes are preferably used because they easily suppress foaming of the resin particles when discharged into the water stream from the small holes of the die. The amount of the foaming agent contained in the polystyrene resin is in the range of 3 to 10 parts by mass, more preferably in the range of 4 to 7 parts by mass with respect to 100 parts by mass of the polystyrene resin.
本発明の盛土用部材製造用発泡性ポリスチレン系樹脂粒子は、必要に応じて前記難燃剤及び発泡剤以外にも、発泡性ポリスチレン系樹脂粒子の製造において一般的に使用されている他の添加剤、例えば、タルク、珪酸カルシウム、合成あるいは天然に産出される二酸化ケイ素、エチレンビスステアリン酸アミド、メタクリル酸エステル系共重合体等の発泡核剤、ジフェニルアルカン、ジフェニルアルケン等の難燃助剤、カーボンブラック、酸化鉄、グラファイト等の着色剤、フェノール系酸化防止剤、硫黄系酸化防止剤、リン系酸化防止剤等の酸化防止剤、ヒンダードアミン類等の安定剤、紫外線吸収剤、酸化防止剤などの添加剤を、ポリスチレン系樹脂中に添加することができる。 In addition to the flame retardant and foaming agent, the foamable polystyrene resin particles for producing embankment members according to the present invention may be added to other additives generally used in the production of expandable polystyrene resin particles. For example, talc, calcium silicate, synthetic or naturally produced silicon dioxide, ethylene bisstearic acid amide, foaming nucleating agent such as methacrylic acid ester copolymer, flame retardant aid such as diphenylalkane and diphenylalkene, carbon Colorants such as black, iron oxide and graphite, phenolic antioxidants, sulfur antioxidants, antioxidants such as phosphorus antioxidants, stabilizers such as hindered amines, UV absorbers, antioxidants, etc. Additives can be added to the polystyrene-based resin.
図１に示す製造装置を用い、本発明の盛土用部材製造用発泡性ポリスチレン系樹脂粒子を製造するには、まず、原料のポリスチレン系樹脂、前記難燃剤、発泡核剤、必要に応じて添加される所望の添加剤を秤量し、原料供給ホッパー３から押出機１内に投入する。原料のポリスチレン系樹脂は、ペレット状や顆粒状にして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。また、複数のロットのリサイクル原料を組み合わせて使用する場合には、複数のロットの原料を事前に良く混合し、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。 In order to produce the expandable polystyrene resin particles for embankment production according to the present invention using the production apparatus shown in FIG. 1, first, the raw material polystyrene resin, the flame retardant, the foam nucleating agent, and optionally added The desired additive is weighed and charged into the extruder 1 from the raw material supply hopper 3. The raw polystyrene resin may be pelletized or granulated and mixed well in advance and then fed from one raw material supply hopper. For example, when multiple lots are used, the supply amount for each lot may be reduced. A plurality of adjusted raw material supply hoppers may be charged and mixed in an extruder. Also, when using a combination of recycled materials from multiple lots, mix the raw materials from multiple lots in advance and remove foreign matter using appropriate sorting methods such as magnetic sorting, sieving, specific gravity sorting, and air blowing sorting. It is preferable to keep it.
本発明の好ましい実施形態において、前記難燃剤を添加する場合、樹脂中に所定濃度で難燃剤を含むマスターバッチ材を用い、これをポリスチレン系樹脂とともに樹脂供給装置内に供給し、該装置内で溶融混練することが好ましい。樹脂中に所定濃度で前記難燃剤を含むマスターバッチ材を前記ポリスチレン系樹脂とともに樹脂供給装置内に供給し、該装置内で溶融混練することによって、難燃剤をより均一に樹脂粒子に含有させることができる。 In a preferred embodiment of the present invention, when the flame retardant is added, a masterbatch material containing a flame retardant at a predetermined concentration in the resin is used, and this is supplied into the resin supply apparatus together with the polystyrene-based resin. It is preferable to melt and knead. A master batch material containing the flame retardant at a predetermined concentration in the resin is supplied into the resin supply apparatus together with the polystyrene resin, and melt-kneaded in the apparatus so that the flame retardant is more uniformly contained in the resin particles. Can do.
押出機１内にポリスチレン系樹脂と難燃剤、さらに発泡助剤やその他の添加剤を供給後、樹脂を加熱溶融し、その難燃剤含有溶融樹脂をダイ２側に移送しながら、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、難燃剤含有溶融樹脂に発泡剤を混合し、押出機１内に必要に応じて設けられる異物除去用のスクリーンを通して、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。
After supplying polystyrene-based resin and flame retardant, further foaming aid and other additives into the extruder 1, the resin is heated and melted, and the flame retardant-containing molten resin is transferred to the
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盛土用部材製造用発泡性ポリスチレン系樹脂粒子となる。
The resin discharge surface in which the small holes of the
形成された盛土用部材製造用発泡性ポリスチレン系樹脂粒子は、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、ここで盛土用部材製造用発泡性ポリスチレン系樹脂粒子を冷却水と分離すると共に脱水乾燥する。乾燥された盛土用部材製造用発泡性ポリスチレン系樹脂粒子は、貯留容器１１に貯留される。
The formed expandable polystyrene resin particles for producing embankment members are transported from the cutting chamber 7 to the flow of cooling water and carried to the dehydrating
前述したように製造された盛土用部材製造用発泡性ポリスチレン系樹脂粒子は、難燃剤及び発泡剤を含有するポリスチレン系樹脂を粒子状としてなり、前記難燃剤は、分子内に臭素原子を有し、臭素分含有量が７０質量％未満であり、分子内にベンゼン環を有し、且つ該難燃剤の５質量％分解温度が２００〜３００℃の範囲内であることを特徴とする。 Expandable polystyrene resin particles for embankment member production as described above are made into a particulate polystyrene resin containing a flame retardant and a foaming agent, and the flame retardant has a bromine atom in the molecule. The bromine content is less than 70% by mass, the molecule has a benzene ring, and the flame retardant has a 5% by mass decomposition temperature in the range of 200 to 300 ° C.
本発明の盛土用部材製造用発泡性ポリスチレン系樹脂粒子は、前記難燃剤が樹脂粒子内に均一に含有されている。本発明の盛土用部材製造用発泡性ポリスチレン系樹脂粒子において、均一に含有されていないと、得られる発泡成形体（盛土用部材）の機械強度、成形性、寸法安定性及び難燃性が劣る恐れがある。 In the expandable polystyrene resin particles for producing embankment members of the present invention, the flame retardant is uniformly contained in the resin particles. If the foamable polystyrene resin particles for producing embankment members of the present invention are not evenly contained, the mechanical strength, moldability, dimensional stability and flame retardancy of the obtained foamed molded product (embankment member) are poor. There is a fear.
本発明の盛土用部材製造用発泡性ポリスチレン系樹脂粒子に用いる前記難燃剤は、環境や生物に対する安全性が高いものであり、特に、テトラブロモビスフェノールＡ誘導体は、ポリスチレン系樹脂発泡成形体に添加した場合に十分な難燃性能を付与でき、環境や生物に対する安全性が高い。
本発明の盛土用部材製造用発泡性ポリスチレン系樹脂粒子は、樹脂粒子中に難燃剤が均一に存在しており、樹脂粒子中に難燃剤が不均一に存在しているものと比べ、得られる盛土用部材の機械強度が高くなり、成形性や寸法安定性にも優れた盛土用部材が得られる。
The flame retardant used in the expandable polystyrene resin particles for producing embankment members according to the present invention is highly safe for the environment and living organisms. In particular, the tetrabromobisphenol A derivative is added to the polystyrene resin foam molded article. In this case, sufficient flame retardancy can be imparted, and the environment and organisms are highly safe.
The expandable polystyrene resin particles for producing embankment members of the present invention are obtained in comparison with those in which the flame retardant is uniformly present in the resin particles and the flame retardant is non-uniformly present in the resin particles. The embedding member has high mechanical strength, and an embedding member having excellent moldability and dimensional stability can be obtained.
本発明に係る製造方法において、原料であるポリスチレン系樹脂として、スチレン系モノマー、エチルベンゼン、イソプロピルベンゼン、ノルマルプロピルベンゼン、キシレン、トルエン、ベンゼンからなる芳香族有機化合物の含有量が低い樹脂原料を選択すれば、製造工程中で前記芳香族有機化合物を混入させることなく盛土用部材製造用発泡性ポリスチレン系樹脂粒子を得ることができるので、得られた盛土用部材製造用発泡性ポリスチレン系樹脂粒子は、前記芳香族有機化合物の含有総量を５００ｐｐｍ未満とすることができる。前記芳香族有機化合物の含有総量は、４５０ｐｐｍ以下であることがより好ましく、４００ｐｐｍ以下であることが更に好ましい。前記芳香族有機化合物の含有総量が低ければ、得られる盛土用部材の機械強度が高くなり、寸法変化率が低いものとなる。また、近年要望されているシックハウス症候群への対応が可能となり、盛土用部材の保管時の安全性を確保することができる。 In the production method according to the present invention, a resin raw material having a low content of an aromatic organic compound composed of a styrene monomer, ethylbenzene, isopropylbenzene, normal propylbenzene, xylene, toluene, and benzene is selected as a polystyrene resin as a raw material. For example, since it is possible to obtain expandable polystyrene resin particles for embedding member production without mixing the aromatic organic compound in the production process, the obtained expandable polystyrene resin particles for embedding member production are: The total content of the aromatic organic compound can be less than 500 ppm. The total content of the aromatic organic compound is more preferably 450 ppm or less, and still more preferably 400 ppm or less. If the total content of the aromatic organic compound is low, the resulting embankment member has high mechanical strength and a low dimensional change rate. In addition, it is possible to cope with sick house syndrome which has been requested in recent years, and it is possible to ensure safety when storing the embankment member.
なお、本発明において、前記芳香族有機化合物の含有総量は、次の＜揮発性有機化合物（ＶＯＣ）含有量の測定方法＞により測定した値である。
＜揮発性有機化合物（ＶＯＣ）含有量の測定方法＞
発泡性ポリスチレン系樹脂粒子１ｇを精秤し、０．１体積％のシクロペンタノールを含有するジメチルホルムアミド溶液１ｍｌを内部標準液として加えた後、更にジメチルホルムアミド溶液にジメチルホルムアミドを加えて２５ｍｌとして測定溶液を作製し、この測定溶液１．８μｌを２３０℃の試料気化室に供給してガスクロマトグラフで検出された各揮発性有機化合物のチャートを得た。そして予め測定しておいた、各揮発性有機化合物の検量線に基づいて、各チャートから揮発性有機化合物量をそれぞれ算出し、発泡性ポリスチレン樹脂粒子中の揮発性有機化合物量を算出した。
なお、本発明では、前述した揮発性有機化合物（ＶＯＣ）含有量のうち、前記芳香族有機化合物に該当する各揮発性有機化合物量の合計量を「芳香族有機化合物の含有総量」としている。
In the present invention, the total content of the aromatic organic compound is a value measured by the following <Measurement method of volatile organic compound (VOC) content>.
<Measurement method of volatile organic compound (VOC) content>
Weigh accurately 1 g of expandable polystyrene resin particles, add 1 ml of a dimethylformamide solution containing 0.1% by volume of cyclopentanol as an internal standard solution, and then add dimethylformamide to the dimethylformamide solution to measure 25 ml. A solution was prepared, and 1.8 μl of this measurement solution was supplied to a 230 ° C. sample vaporization chamber to obtain a chart of each volatile organic compound detected by a gas chromatograph. And based on the calibration curve of each volatile organic compound measured beforehand, the amount of volatile organic compounds was calculated from each chart, and the amount of volatile organic compounds in the expandable polystyrene resin particles was calculated.
In the present invention, among the volatile organic compound (VOC) contents described above, the total amount of each volatile organic compound corresponding to the aromatic organic compound is defined as “total amount of aromatic organic compound”.
前述した本発明に係る製造方法により得られた盛土用部材製造用発泡性ポリスチレン系樹脂粒子は、発泡樹脂成形体の製造分野において周知の装置及び手法を用い、水蒸気加熱等により加熱して予備発泡し、盛土用部材製造用予備発泡粒子（以下、予備発泡粒子と記す）とする。この予備発泡粒子は、製造するべき発泡成形体（盛土用部材）の密度と同等の嵩密度となるように予備発泡される。本発明において、その嵩密度は限定されないが、０．０１０〜０．０５０ｇ／ｃｍ３の範囲内が好ましく、０．０１５〜０．０３３ｇ／ｃｍ３の範囲内がより好ましい。 The foamable polystyrene resin particles for embankment member production obtained by the production method according to the present invention described above are pre-foamed by heating by steam heating or the like using a well-known apparatus and method in the field of foamed resin molding production. And pre-expanded particles for embankment member production (hereinafter referred to as pre-expanded particles). The pre-expanded particles are pre-expanded so as to have a bulk density equivalent to the density of the foam molded body (filling member) to be manufactured. In the present invention, its bulk density is not limited, preferably in a range of 0.010~0.050g / cm 3, within the scope of 0.015~0.033g / cm 3 is more preferable.
なお、本発明において予備発泡粒子の嵩密度とは、次のようにして測定されたものをいう。
＜予備発泡粒子の嵩密度と嵩発泡倍数＞
先ず、予備発泡粒子を測定試料としてＷｇ採取し、この測定試料をメスシリンダー内に自然落下させた後、メスシリンダーの底をたたいて試料の見掛け体積（Ｖ）ｃｍ３を一定にし、その質量と体積を測定し、下記式に基づいて予備発泡粒子の嵩密度を測定する。
嵩密度（ｇ／ｃｍ３）＝測定試料の質量（Ｗ）／測定試料の体積（Ｖ）
また、予備発泡粒子の嵩発泡倍数は次式により算出される数値である。
嵩発泡倍数（倍）＝１／嵩密度（ｇ／ｃｍ３）
In the present invention, the bulk density of the pre-expanded particles is measured as follows.
<Bulk density and bulk expansion ratio of pre-expanded particles>
First, Wg was sampled from pre-expanded particles as a measurement sample, and this measurement sample was allowed to fall naturally into a graduated cylinder, and then the apparent volume (V) cm 3 of the sample was made constant by tapping the bottom of the graduated cylinder. And the volume is measured, and the bulk density of the pre-expanded particles is measured based on the following formula.
Bulk density (g / cm 3 ) = mass of measurement sample (W) / volume of measurement sample (V)
The bulk expansion ratio of the pre-expanded particles is a numerical value calculated by the following formula.
Bulk foam multiple (times) = 1 / bulk density (g / cm 3 )
前記予備発泡粒子は、発泡樹脂成形体の製造分野において周知の装置及び手法を用い、該予備発泡粒子を成形型のキャビティ内に充填し、水蒸気加熱等により加熱して型内発泡成形し、難燃性ポリスチレン系樹脂発泡成形体からなる盛土用部材を製造する。
本発明の盛土用部材の密度は特に限定されないが、０．０１０〜０．０５０ｇ／ｃｍ３の範囲内が好ましく、０．０１５〜０．０３３ｇ／ｃｍ３の範囲内がより好ましい。
また、盛土用部材の形状・寸法等は特に限定されず、実施する盛土等の工法や規模等に応じて適宜決められ、厚板状、ブロック状、係合溝や突起を有する形状など、種々の大きさや形状とすることができる。
The pre-expanded particles can be obtained by filling the pre-expanded particles into a cavity of a molding die using a well-known apparatus and technique in the field of manufacturing a foamed resin molded body, and heating them by steam heating or the like to perform in-mold foam molding. The embankment member which consists of a flame-retardant polystyrene type resin foam molding is manufactured.
Although the density of the embankment member of the present invention is not particularly limited, but is preferably in the range of 0.010~0.050g / cm 3, within the scope of 0.015~0.033g / cm 3 is more preferable.
In addition, the shape, dimensions, etc. of the embankment member are not particularly limited, and are appropriately determined according to the embedding method to be carried out, the scale, etc. The size and shape can be made.
なお、本発明において盛土用部材の密度とは、ＪＩＳ Ｋ７１２２：１９９９「発泡プラスチック及びゴム−見掛け密度の測定」記載の方法で測定した発泡成形体の密度のことである。
＜発泡成形体の密度と発泡倍数＞
５０ｃｍ３以上（半硬質および軟質材料の場合は１００ｃｍ３以上）の試験片を材料の元のセル構造を変えない様に切断し、その質量を測定し、次式により算出した。
密度（ｇ／ｃｍ３）＝試験片質量（ｇ）／試験片体積（ｃｍ３）
試験片状態調節、測定用試験片は、成形後７２時間以上経過した試料から切り取り、２３℃±２℃×５０％±５％または２７℃±２℃×６５％±５％の雰囲気条件に１６時間以上放置したものである。
また、発泡成形体の発泡倍数は次式により算出される数値である。
発泡倍数（倍）＝１／密度（ｇ／ｃｍ３）
In the present invention, the density of the embankment member is the density of the foamed molded product measured by the method described in JIS K7122: 1999 “Measurement of foamed plastic and rubber-apparent density”.
<Density and expansion ratio of foamed molded product>
A test piece of 50 cm 3 or more (100 cm 3 or more in the case of semi-rigid and soft materials) was cut so as not to change the original cell structure of the material, its mass was measured, and calculated by the following formula.
Density (g / cm 3 ) = Test piece mass (g) / Test piece volume (cm 3 )
Test piece condition adjustment and measurement test pieces were cut out from samples that had passed 72 hours or more after molding, and were subjected to atmospheric conditions of 23 ° C. ± 2 ° C. × 50% ± 5% or 27 ° C. ± 2 ° C. × 65% ± 5%. It has been left for more than an hour.
Further, the expansion factor of the foamed molded product is a numerical value calculated by the following equation.
Foaming multiple (times) = 1 / density (g / cm 3 )
本発明の盛土用部材は、発泡倍数５０倍の発泡成形体について、気泡の平均弦長が４０〜２００μｍの範囲であることが好ましく、５０〜１５０μｍの範囲がより好ましい。なお、本発明において気泡の平均弦長とは、下記の方法で測定した発泡成形体の気泡の平均弦長のことである。
＜平均弦長＞
発泡成形体の気泡の平均弦長は、ＡＳＴＭ Ｄ２８４２−６９の試験方法に準拠して測定されたものをいう。具体的には、発泡成形体を略二等分となるように切断し、切断面を走査型電子顕微鏡（日立製作所社製 商品名「Ｓ−３０００Ｎ］）を用いて１００倍に拡大して撮影する。撮影した画像をＡ４用紙に印刷し、任意の箇所に長さ６０ｍｍの直線を一本描き、この直線上に存在する気泡数から気泡の平均弦長（ｔ）を下記式より算出する。
平均弦長ｔ＝６０／（気泡数×写真の倍率）
なお、直線を描くにあたり、直線が気泡に点接触してしまう場合には、この気泡も気泡数に含め、更に、直線の両端部が気泡を貫通することもなく、気泡内に位置した状態となる場合には、直線の両端部が位置している気泡も気泡数に含める。更に、撮影した画像の任意の５箇所において上述と同様の要領で平均弦長を算出し、これらの平均弦長の相加平均値を発泡成形体の気泡の平均弦長とする。
本発明の盛土用部材は、酸素指数が２６以上であることが好ましい。酸素指数が２６未満であると充分な難燃性が得られないおそれがある。
In the embankment member of the present invention, the average chord length of the bubbles is preferably in the range of 40 to 200 μm, more preferably in the range of 50 to 150 μm, with respect to the foamed molded product having a foaming factor of 50 times. In addition, in this invention, the average chord length of a bubble is an average chord length of the bubble of a foaming molding measured by the following method.
<Average string length>
The average chord length of the bubbles of the foam molded article refers to that measured according to the test method of ASTM D2842-69. Specifically, the foamed molded body is cut into approximately equal halves, and the cut surface is photographed at a magnification of 100 times using a scanning electron microscope (trade name “S-3000N” manufactured by Hitachi, Ltd.). The photographed image is printed on A4 paper, and a straight line having a length of 60 mm is drawn at an arbitrary position, and the average chord length (t) of the bubbles is calculated from the following formula from the number of bubbles existing on the straight line.
Average string length t = 60 / (number of bubbles × photo magnification)
When drawing a straight line, if the straight line is in point contact with the bubble, this bubble is included in the number of bubbles, and both ends of the straight line are not penetrating the bubble and are in the bubble. In this case, the bubbles in which both ends of the straight line are positioned are included in the number of bubbles. Further, the average chord length is calculated in the same manner as described above at any five locations in the photographed image, and the arithmetic mean value of these average chord lengths is set as the average chord length of the bubbles of the foam molded body.
The embankment member of the present invention preferably has an oxygen index of 26 or more. If the oxygen index is less than 26, sufficient flame retardancy may not be obtained.
［実施例１］
（発泡性ポリスチレン系樹脂粒子の製造）
基材樹脂としてポリスチレン樹脂（東洋スチレン社製、商品名「ＨＲＭ−１０Ｎ」）１００質量部に対して、難燃剤として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）（第一工業製薬社製）を５０質量％含むポリスチレン樹脂マスターバッチ７質量部（難燃剤量で３．５質量部相当）、微粉末タルク０．７質量部を、予めタンブラーミキサーにて均一に混合したものを、時間当たり１６０ｋｇ／ｈｒの割合で口径９０ｍｍの単軸押出機内へ供給し、樹脂を加熱溶融させた後、発泡剤として樹脂１００質量部に対して６質量部のイソペンタンを押出機途中より圧入した。そして、押出機内で樹脂と発泡剤を混練しつつ、押出機先端部での樹脂温度が１９０℃となるように冷却しながら、押出機に連接しヒーターにより３２０℃に保持した、直径０．６ｍｍ、ランド長さ３．０ｍｍのノズルを２００個有する造粒用ダイスを通して、３０℃の冷却水が循環するチャンバー内に押し出すと同時に、円周方向に１０枚の刃を有する高速回転カッターをダイスに密着させて、毎分３０００回転で切断し、脱水乾燥して球形の発泡性ポリスチレン樹脂粒子を得た。得られた発泡性樹脂粒子は変形、ヒゲ等の発生もなく、平均粒径１．１ｍｍであった。
得られた発泡性ポリスチレン系樹脂粒子１００質量部に対して、ポリエチレングリコール０．０３質量部、ステアリン酸亜鉛０．１５質量部、ステアリン酸モノグリセライド０．０５質量部、ヒドロキシステアリン酸トリグリセライド０．０５質量部を発泡性ポリスチレン系樹脂粒子の表面全面に均一に被覆した。
[Example 1]
(Manufacture of expandable polystyrene resin particles)
Tetrabromobisphenol A-bis (2,3-dibromo-2-methylpropyl ether) as a flame retardant with respect to 100 parts by mass of a polystyrene resin (trade name “HRM-10N” manufactured by Toyo Styrene Co., Ltd.) as a base resin 7 parts by mass of a polystyrene resin masterbatch (made by Daiichi Kogyo Seiyaku Co., Ltd.) containing 50% by mass (corresponding to 3.5 parts by mass of flame retardant) and 0.7 parts by mass of fine powder talc are uniformly mixed in advance using a tumbler mixer. After being fed into a single-screw extruder with a diameter of 90 mm at a rate of 160 kg / hr per hour, the resin is heated and melted, and then 6 parts by mass of isopentane as a foaming agent is added to the resin in the middle of the extruder. More press fit. Then, while kneading the resin and the foaming agent in the extruder, while cooling so that the resin temperature at the tip of the extruder is 190 ° C., it is connected to the extruder and held at 320 ° C. by a heater, diameter 0.6 mm Then, through a granulation die having 200 nozzles with a land length of 3.0 mm, it is extruded into a chamber in which cooling water at 30 ° C. circulates, and at the same time, a high-speed rotary cutter having 10 blades in the circumferential direction is used as the die Adhered, cut at 3000 rpm, dehydrated and dried to obtain spherical expandable polystyrene resin particles. The obtained expandable resin particles had no average deformation and no whisker, and had an average particle size of 1.1 mm.
Polyethylene glycol 0.03 parts by mass, zinc stearate 0.15 parts by mass, stearic acid monoglyceride 0.05 parts by mass, hydroxystearic acid triglyceride 0.05 parts by mass with respect to 100 parts by mass of the obtained expandable polystyrene resin particles. The part was uniformly coated on the entire surface of the expandable polystyrene resin particles.
（発泡成形体の製造）
前記の通り製造した発泡性ポリスチレン系樹脂粒子は、１５℃の保冷庫中に入れ、７２時間に亘って放置した後、円筒型バッチ式予備発泡機に供給して、吹き込み圧０．０５ＭＰａの水蒸気により加熱し、予備発泡粒子を得た。得られた予備発泡粒子は、嵩密度０．０１５ｇ／ｃｍ３（嵩発泡倍数６７倍）であった。続いて、得られた予備発泡粒子を室温雰囲気下、２４時間に亘って放置した後、長さ４００ｍｍ×幅３００ｍｍ×高さ５０ｍｍの長方形状のキャビティを有する成形型内に予備発泡粒子を充填し、その後、成形型のキャビティ内を水蒸気でゲージ圧０．０８ＭＰａの圧力で２０秒間に亘って加熱し、その後、成形型のキャビティ内の圧力が０．０１ＭＰａになるまで冷却し、その後成形型を開き、長さ４００ｍｍ×幅３００ｍｍ×高さ５０ｍｍの長方形状の発泡成形体を取り出した。 得られた発泡成形体は、密度０．０１５ｇ／ｃｍ３（発泡倍数６７倍）であった。
(Manufacture of foam moldings)
The expandable polystyrene resin particles produced as described above are placed in a 15 ° C. cool box and allowed to stand for 72 hours, and then supplied to a cylindrical batch type pre-foaming machine to generate steam with a blowing pressure of 0.05 MPa. To obtain pre-expanded particles. The obtained pre-expanded particles had a bulk density of 0.015 g / cm 3 (bulk expansion ratio: 67 times). Subsequently, the pre-expanded particles obtained were allowed to stand at room temperature for 24 hours, and then the pre-expanded particles were filled into a mold having a rectangular cavity of length 400 mm × width 300 mm × height 50 mm. Thereafter, the inside of the cavity of the mold is heated with water vapor at a gauge pressure of 0.08 MPa for 20 seconds, and then cooled until the pressure in the cavity of the mold reaches 0.01 MPa. Opened, a rectangular foam molded body having a length of 400 mm, a width of 300 mm, and a height of 50 mm was taken out. The obtained foamed molded product had a density of 0.015 g / cm 3 (foaming factor 67 times).
前述した通り製造した実施例１の発泡性ポリスチレン系樹脂粒子、予備発泡粒子及び発泡成形体について、以下の評価試験を行った。 The following evaluation tests were performed on the expandable polystyrene resin particles, pre-expanded particles, and expanded molded articles of Example 1 produced as described above.
＜難燃剤の分解温度の測定＞
難燃剤組成物を２０ｍｇ採取して試料とし、示差熱・熱量同時測定装置 ＴＧ／ＤＴＡ ３００型（セイコー電子工業社製）を用いて、窒素ガス量３０ミリリットル／分、加熱温度１０℃／分、測定温度３０〜８００℃の条件下にて試料の質量減少率を測定し、縦軸に試料の質量減少率を、横軸に温度をとったグラフを得る。そして、得られたグラフに基づいて、試料の質量減少率が５％に達した時の温度を「５質量％分解温度」とした。
<Measurement of flame retardant decomposition temperature>
20 mg of the flame retardant composition was sampled and used as a sample, using a differential heat and calorie simultaneous measurement device TG / DTA 300 type (manufactured by Seiko Denshi Kogyo Co., Ltd.), a nitrogen gas amount of 30 ml / min, a heating temperature of 10 ° C./min, The mass reduction rate of the sample is measured at a measurement temperature of 30 to 800 ° C., and a graph is obtained with the mass reduction rate of the sample on the vertical axis and the temperature on the horizontal axis. And based on the obtained graph, the temperature when the mass reduction rate of the sample reached 5% was defined as “5 mass% decomposition temperature”.
＜ビーズ発泡性の評価＞
実施例（及び比較例）で得られた発泡性ポリスチレン系樹脂粒子を１５℃の保冷庫に７２時間保管した後、これを円筒型バッチ式予備発泡機に供給して、吹き込み蒸気圧０．０５ＭＰａの水蒸気により２分間に亘って加熱し、得られた予備発泡粒子の嵩発泡倍数を下記の通り測定し、次の評価基準：
嵩発泡倍数６０倍以上を○（良）、
嵩発泡倍数５０倍以上６０倍未満を△（やや良）、
嵩発泡倍数５０倍未満を×（不良）、に照らし、ビーズ発泡性の評価を行った。
<Evaluation of bead foamability>
After the expandable polystyrene resin particles obtained in the examples (and comparative examples) were stored in a 15 ° C. cool box for 72 hours, this was supplied to a cylindrical batch type pre-foaming machine, and the blowing vapor pressure was 0.05 MPa. The pre-expanded particles obtained were heated for 2 minutes with water vapor and the bulk expansion ratio of the pre-expanded particles was measured as follows, and the following evaluation criteria:
○ (good) when the foam expansion ratio is 60 times or more
△ (slightly good) when the bulk expansion ratio is 50 times or more and less than 60 times,
The bead foaming property was evaluated in light of x (defective) when the bulk expansion ratio was less than 50 times.
＜難燃性の評価＞
得られた発泡成形体から、厚み１０ｍｍ×長さ１５０ｍｍ×幅１０ｍｍの大きさの試験片をバーチカルカッターにて切り出し、５０℃オーブンにて７日間養生した後、温度２３℃、相対湿度５０％にて４日間状態調節し、ＪＩＳ Ｋ７２０１に準じて酸素指数を測定し、下記の基準に基づいて難燃性を評価した。
○（良）・・・酸素指数が２６以上
×（不良）・・・酸素指数が２６未満
<Evaluation of flame retardancy>
A test piece having a thickness of 10 mm, a length of 150 mm, and a width of 10 mm was cut out from the obtained foamed molded article with a vertical cutter, cured in a 50 ° C. oven for 7 days, and then adjusted to a temperature of 23 ° C. and a relative humidity of 50%. The condition was adjusted for 4 days, the oxygen index was measured according to JIS K7201, and the flame retardancy was evaluated based on the following criteria.
○ (Good): Oxygen index is 26 or more x (Poor): Oxygen index is less than 26
＜発泡成形体の外観評価＞
上記ポリスチレン系樹脂予備発泡粒子を発泡成形機の金型に充填し、水蒸気を用いて二次発泡させることによって長さ４００ｍｍ、幅３００ｍｍ、厚み５０ｍｍの直方体状の発泡成形体を得た。
発泡成形体の外観を目視観察し、下記の基準に基づいて評価をした。
◎（極めて良）：発泡粒子間の間隙がなく、表面が極めて平滑な状態である。
○（良）：発泡粒子間の間隙がなく、表面が平滑な状態である。
△（やや良）：発泡粒子間の間隙が少なく、表面の平滑が少し劣る。
×（不良）：発泡粒子間の間隙が大きく、表面の平滑がかなり劣る。
<Appearance evaluation of foam molding>
The polystyrene resin pre-expanded particles were filled into a mold of a foam molding machine and subjected to secondary foaming using water vapor to obtain a rectangular foam-shaped foam molded body having a length of 400 mm, a width of 300 mm, and a thickness of 50 mm.
The appearance of the foamed molded product was visually observed and evaluated based on the following criteria.
A (very good): There is no gap between the expanded particles, and the surface is very smooth.
○ (good): There is no gap between the expanded particles, and the surface is smooth.
Δ (slightly good): There are few gaps between the expanded particles, and the surface smoothness is slightly inferior.
X (Poor): The gap between the expanded particles is large, and the smoothness of the surface is considerably inferior.
＜総合評価＞
前記＜ビーズ発泡性の評価＞、＜難燃性の評価＞及び＜発泡成形体の外観評価＞の各評価項目について、不良（×）が無いものを良（○）とし、１つ以上不良（×）が有るものを不良（×）として総合評価した。
<Comprehensive evaluation>
Regarding each of the evaluation items of <Bead Foaming Evaluation>, <Flame Retardancy Evaluation>, and <Foam Molded Body Appearance Evaluation> Those having x) were comprehensively evaluated as defective (x).
［実施例２］
難燃剤として、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）（第一工業製薬社製）を同量用いたこと以外は、実施例１と同様にして発泡倍数６７倍の発泡成形体を製造した。
[Example 2]
As the flame retardant, foam molding with an expansion ratio of 67 times was performed in the same manner as in Example 1 except that the same amount of tetrabromobisphenol A-bis (2,3-dibromopropyl ether) (Daiichi Kogyo Seiyaku Co., Ltd.) was used. The body was manufactured.
［実施例３］
難燃剤として、テトラブロモビスフェノールＡ−ビス（アリルエーテル）（第一工業製薬社製）を同量用いたこと以外は、実施例１と同様にして発泡倍数６７倍の発泡成形体を製造した。
[Example 3]
A foamed molded article having a foam expansion factor of 67 times was produced in the same manner as in Example 1 except that the same amount of tetrabromobisphenol A-bis (allyl ether) (Daiichi Kogyo Seiyaku Co., Ltd.) was used as the flame retardant.
［実施例４］
難燃剤として、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）３．２質量部、テトラブロモビスフェノールＡ−ビス（アリルエーテル）０．３質量部を混合して用いたこと以外は、実施例１と同様にして発泡倍数６７倍の発泡成形体を製造した。
[Example 4]
Except that 3.2 parts by mass of tetrabromobisphenol A-bis (2,3-dibromopropyl ether) and 0.3 parts by mass of tetrabromobisphenol A-bis (allyl ether) were used as flame retardants, In the same manner as in Example 1, a foamed molded article having a foam multiple of 67 times was produced.
［実施例５］
難燃剤Ａの配合量を５．０質量部としたこと以外は、実施例１と同様にして発泡倍数６７倍の発泡成形体を製造した。
[Example 5]
A foamed molded article having a foam multiple of 67 times was produced in the same manner as in Example 1 except that the blending amount of the flame retardant A was 5.0 parts by mass.
［比較例１］
難燃剤として、ヘキサブロモシクロドデカン（第一工業製薬社製）を同量用いたこと以外は、実施例１と同様にして発泡成形体を製造した。
[Comparative Example 1]
A foamed molded article was produced in the same manner as in Example 1 except that the same amount of hexabromocyclododecane (Daiichi Kogyo Seiyaku Co., Ltd.) was used as the flame retardant.
［比較例２］
難燃剤として、トリス−（２，３−ジブロモプロピル）イソシアヌレート（日本化成社製）を同量用いたこと以外は、実施例１と同様にして発泡成形体を製造した。
[Comparative Example 2]
A foamed molded article was produced in the same manner as in Example 1 except that the same amount of tris- (2,3-dibromopropyl) isocyanurate (Nihon Kasei Co., Ltd.) was used as the flame retardant.
［比較例３］
難燃剤として、ペンタブロモベンジルアクリレート（第一工業製薬社製）を同量用いたこと以外は、実施例１と同様にして発泡成形体を製造した。
[Comparative Example 3]
A foamed molded article was produced in the same manner as in Example 1 except that the same amount of pentabromobenzyl acrylate (Daiichi Kogyo Seiyaku Co., Ltd.) was used as the flame retardant.
［比較例４］
難燃剤として、トリス（トリブロモネオペンチル）フォスフェート（大八化学社製）を同量用いたこと以外は、実施例１と同様にして発泡成形体を製造した。
[Comparative Example 4]
A foamed molded article was produced in the same manner as in Example 1 except that the same amount of tris (tribromoneopentyl) phosphate (manufactured by Daihachi Chemical Co., Ltd.) was used as a flame retardant.
前記実施例１〜５及び比較例１〜４で用いた難燃剤の臭素分含有量、難燃剤分子中ベンゼン環の有無、５質量％分解温度を表１にまとめて記す。
また、前記実施例１〜５及び比較例１〜４の測定・評価結果を表２にまとめて記す。
Table 1 summarizes the bromine content of the flame retardants used in Examples 1 to 5 and Comparative Examples 1 to 4, the presence or absence of a benzene ring in the flame retardant molecule, and the 5 mass% decomposition temperature.
Moreover, the measurement and evaluation results of Examples 1 to 5 and Comparative Examples 1 to 4 are summarized in Table 2.
表１，２の結果より、実施例分子内に臭素原子を有し、臭素分含有量が７０質量％未満であり、分子内にベンゼン環を有し、且つ該難燃剤の５質量％分解温度が２００〜３００℃の範囲内である難燃剤Ａ〜Ｃを用いた、本発明に係る実施例１〜５は、ビーズ発泡性、難燃性及び発泡体の外観がいずれも良好であった。
一方、臭素分含有量が７５質量％と多く、分子中にベンゼン環の無い難燃剤Ｄを用いた比較例１は、ビーズ発泡性が不良であった。
また、分子中にベンゼン環の無い難燃剤Ｅを用いた比較例２は、ビーズ発泡性、発泡体の外観が不良となった。
また、臭素分含有量が７５質量％と多く、５質量％分解温度が３００℃を超える難燃剤Ｆを用いた比較例３は、難燃性が不良となった。
また、臭素分含有量が７５質量％と多く、分子中にベンゼン環が無く、５質量％分解温度が３００℃を超える難燃剤Ｇを用いた比較例４は、ビーズ発泡性、難燃性、発泡体の外観のいずれも不良となった。
From the results of Tables 1 and 2, the examples have bromine atoms in the molecule, the bromine content is less than 70% by mass, the molecule has a benzene ring, and the flame retardant has a 5% by mass decomposition temperature. In Examples 1 to 5 according to the present invention using the flame retardants A to C in the range of 200 to 300 ° C., the bead foamability, flame retardancy, and the appearance of the foam were all good.
On the other hand, Comparative Example 1 using the flame retardant D having a high bromine content of 75% by mass and having no benzene ring in the molecule had poor bead foaming properties.
In Comparative Example 2 using the flame retardant E having no benzene ring in the molecule, the bead foaming property and the appearance of the foam were poor.
In addition, Comparative Example 3 using the flame retardant F having a high bromine content of 75% by mass and a 5% by mass decomposition temperature exceeding 300 ° C. had poor flame retardancy.
Comparative Example 4 using a flame retardant G having a high bromine content of 75% by mass, no benzene ring in the molecule and a 5% by mass decomposition temperature exceeding 300 ° C. All of the foam appearances were poor.
本発明は、環境や生物に対する安全性が高い難燃剤を用いて十分な難燃性能を有し、機械強度・成形性・外観にも優れた難燃性ポリスチレン系樹脂発泡成形体、該成形体の製造に用いる盛土用部材製造用発泡性ポリスチレン系樹脂粒子とその製造方法に関する。本発明の盛土用部材は、軟弱地盤上や傾斜地での盛土や、庭園の築山での盛土、更には地下構造物の埋込み、埋戻し等に好適に使用される。 The present invention relates to a flame-retardant polystyrene resin foam molded article having sufficient flame retardancy using a flame retardant having high safety to the environment and living organisms and excellent in mechanical strength, moldability and appearance, and the molded article The present invention relates to an expandable polystyrene resin particle for use in the production of embankment members and a method for producing the same. The embankment member of the present invention is suitably used for embankment on soft ground or on sloping ground, embankment in the construction of gardens, and embedding and backfilling of underground structures.
１…押出機（樹脂供給装置）、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…貯留容器。 DESCRIPTION OF SYMBOLS 1 ... Extruder (resin supply apparatus), 2 ... Die, 3 ... Raw material supply hopper, 4 ... High pressure pump, 5 ... Foam supply port, 6 ... Cutter, 7 ... Cutting chamber, 8 ... Water tank, 9 ... High pressure pump, 10: Dehydration dryer with solid-liquid separation function, 11: Storage container.
Claims (11)
前記難燃剤は、分子内に臭素原子を有し、臭素分含有量が７０質量％未満であり、分子内にベンゼン環を有し、且つ該難燃剤の５質量％分解温度が２００〜３００℃の範囲内であり、
樹脂供給装置内でポリスチレン系樹脂に難燃剤及び発泡剤を添加、混練し、難燃剤・発泡剤含有の溶融樹脂を樹脂供給装置先端に付設されたダイの小孔から直接冷却用液体中に押し出し、押し出すと同時に押出物を切断するとともに、押出物を液体との接触により冷却固化して発泡性ポリスチレン系樹脂粒子を得る溶融押出法により得られたものであることを特徴とする盛土用部材製造用発泡性ポリスチレン系樹脂粒子。 Expandable polystyrene resin particles for producing a material for embankment in which a polystyrene resin containing a flame retardant and a foaming agent is in the form of particles,
The flame retardant has a bromine atom in the molecule, a bromine content of less than 70% by mass, a benzene ring in the molecule, and a 5% by mass decomposition temperature of the flame retardant of 200 to 300 ° C. Within the range of
Add and knead the flame retardant and foaming agent to the polystyrene resin in the resin supply unit, and extrude the flame retardant / foaming agent-containing molten resin directly into the cooling liquid from the small hole in the die attached to the tip of the resin supply unit The material for embankment is obtained by a melt extrusion method in which extrudate is cut at the same time as extrusion and the extrudate is cooled and solidified by contact with a liquid to obtain expandable polystyrene resin particles. Expandable polystyrene resin particles.
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| JP2009246292A JP2011093949A (en) | 2009-10-27 | 2009-10-27 | Foamable polystyrene resin particles for production of banking member and process for production thereof, prefoamed particles for production of banking member, and banking member |
| PCT/JP2010/069053 WO2011052631A1 (en) | 2009-10-27 | 2010-10-27 | Foamable polystyrene resin particles and process for production thereof, polystyrene resin prefoamed particles, polystyrene resin foam-molded article, heat-insulating material for building material, banking member, and vehicle interior material |
| CN2010800596359A CN102686654A (en) | 2009-10-27 | 2010-10-27 | Foamable polystyrene resin particles and process for production thereof, polystyrene resin prefoamed particles, polystyrene resin foam-molded article, heat-insulating material for building material, banking member, and vehicle interior material |
| TW099136662A TWI439503B (en) | 2009-10-27 | 2010-10-27 | Expandable polystyrene type resin pellets and production method thereof, polystyrene type resin pre- expanded particle, polystyrene type resin expanded form, insulator for building material, banking material, and interior material for vehicle |
| EP10826763.4A EP2495277B1 (en) | 2009-10-27 | 2010-10-27 | Foamable polystyrene resin particles and process for production thereof, polystyrene resin prefoamed particles, polystyrene resin foam-molded article, heat-insulating material for building material, banking member, and vehicle interior material |
| US13/504,072 US20120214885A1 (en) | 2009-10-27 | 2010-10-27 | Foamable polystyrene resin particles and process for production thereof, polystyrene resin prefoamed particles, polystyrene resin foam-molded article, heat-insulating material for building material, banking member, and vehicle interior material |
| CN201610046400.5A CN105542216A (en) | 2009-10-27 | 2010-10-27 | Heat-insulating material for building material, earth-filling member, and vehicle interior material |
| US15/098,702 US20160229974A1 (en) | 2009-10-27 | 2016-04-14 | Foamable polystyrene resin particles and polystyrene resin prefoamed particles |
| US15/617,823 US10358538B2 (en) | 2009-10-27 | 2017-06-08 | Foamable polystyrene resin particles and polystyrene resin prefoamed particles |
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