JP2022186193A - Foamable styrenic resin particle, and method for producing foamable styrenic resin particle - Google Patents
Foamable styrenic resin particle, and method for producing foamable styrenic resin particle Download PDFInfo
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- JP2022186193A JP2022186193A JP2021094290A JP2021094290A JP2022186193A JP 2022186193 A JP2022186193 A JP 2022186193A JP 2021094290 A JP2021094290 A JP 2021094290A JP 2021094290 A JP2021094290 A JP 2021094290A JP 2022186193 A JP2022186193 A JP 2022186193A
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- weight
- expandable styrene
- resin particles
- parts
- styrene resin
- Prior art date
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 232
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- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- WPZJSWWEEJJSIZ-UHFFFAOYSA-N tetrabromobisphenol-F Natural products C1=C(Br)C(O)=C(Br)C=C1CC1=CC(Br)=C(O)C(Br)=C1 WPZJSWWEEJJSIZ-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- VLPFTAMPNXLGLX-UHFFFAOYSA-N trioctanoin Chemical compound CCCCCCCC(=O)OCC(OC(=O)CCCCCCC)COC(=O)CCCCCCC VLPFTAMPNXLGLX-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
本発明は、発泡性スチレン系脂粒子と、その製造方法に関する。 TECHNICAL FIELD The present invention relates to expandable styrene-based fat particles and a method for producing the same.
発泡性スチレン系樹脂粒子は、発泡剤（易揮発性の脂肪族炭化水素、例えばブタン、ペンタン等）を含浸されているので、比較的安価で、特殊な方法を用いずに蒸気等で発泡成形ができ、高い緩衝・断熱の効果が得られる為、社会的に有用な材料である。得られた発泡成形体は、魚箱、農産箱、食品用容器、家電製品等の緩衝材、建材用断熱材等の幅広い用途に使用されている。 Expandable styrene resin particles are impregnated with a blowing agent (easily volatile aliphatic hydrocarbon such as butane, pentane, etc.), so they are relatively inexpensive and can be foamed by steam or the like without using a special method. It is a socially useful material because it can provide high cushioning and heat insulation effects. The resulting foamed molded product is used in a wide range of applications, such as fish boxes, agricultural product boxes, food containers, cushioning materials for home electric appliances and the like, and heat insulating materials for building materials.
発泡性スチレン系樹脂成形体を工業的および経済的に製造する方法としては、(1) 発泡性スチレン系樹脂粒子を、水蒸気等の加熱媒体を用いて予備発泡粒子とし、(2) 当該予備発泡粒子を、所望の形状を有する、壁面に多数の小孔が穿設された閉鎖型の金型内に充填し、(3) 当該金型の小孔から水蒸気等の加熱媒体を導入して予備発泡粒子をその軟化点以上の温度に加熱し、予備発泡粒子を互いに融着させて成形し、(4) 冷却した後、金型内から取り出す方法が一般的である。 As a method for industrially and economically producing an expandable styrene-based resin molded article, (1) expandable styrene-based resin particles are pre-expanded using a heating medium such as steam, and (2) the pre-expanded particles are prepared. The particles are filled in a closed mold having a desired shape and having a large number of small holes in the wall surface, and (3) a heating medium such as steam is introduced from the small holes of the mold to prepare A common method is to heat the expanded particles to a temperature above their softening point, fuse the pre-expanded particles to form a mold, (4) cool, and then remove from the mold.
前記予備発泡粒子を得る段階では、発泡性スチレン系樹脂粒子を、ブロッキング抑制剤や融着促進剤等の、粉体状の外添剤で被覆することで、例えば、予備発泡粒子同士が結合した状態（ブロッキングという）となることを解消している。例えば、特許文献１では、樹脂粒子本体表面にポリエーテル、及び、タルクやシリカ等の粉末状無機物又は有機物を塗布することによって、予備発泡工程でのブロッキングを防止することが提案されている。 In the step of obtaining the pre-expanded particles, the expandable styrene-based resin particles are coated with a powdery external additive such as a blocking inhibitor and a fusion promoter, so that the pre-expanded particles are bonded to each other, for example. It eliminates the state (called blocking). For example, Patent Document 1 proposes to prevent blocking in the pre-foaming step by applying polyether and a powdery inorganic or organic substance such as talc or silica to the surface of the resin particle body.
ここで、発泡性スチレン系樹脂粒子から、粉状の添付剤が剥離することにより、当該樹脂粒子の空気輸送に用いられる装置のフィルターの詰まりや、成形時に金型の小孔が詰まる等の不具合や、発泡成形体の強度低下等の問題が生じることがある。 Here, when the powdery adhesive is peeled off from the expandable styrene resin particles, problems such as clogging of the filter of the device used for pneumatic transportation of the resin particles and clogging of the small holes of the mold during molding are caused. Also, problems such as a decrease in the strength of the foam molded product may occur.
このような問題を解決する方法として、特許文献２では、樹脂粒子本体に、酸化マグネシウムやタルク等の難水溶性無機物、及び、液状の脂肪酸トリグリセリドを塗布することで、予備発泡工程でのブロッキングを防止し、かつ、塗布剤の剥がれを防止することが提案されている。
特許文献３には、樹脂粒子本体表面にメチルフェニルシリコーンオイル、および高級脂肪酸の金属塩を塗布することで、予備発泡工程でのブロッキングを防止、塗布剤の剥がれを防止することが提案されている。
As a method for solving such a problem, in Patent Document 2, blocking in the pre-foaming step is prevented by applying a poorly water-soluble inorganic substance such as magnesium oxide or talc, and a liquid fatty acid triglyceride to the resin particle body. It has been proposed to prevent this and prevent the peeling of the coating.
Patent Document 3 proposes to prevent blocking in the prefoaming step and to prevent peeling of the coating agent by applying methylphenyl silicone oil and a metal salt of a higher fatty acid to the surface of the resin particle body. .
しかしながら、特許文献１～３に記載の発泡性ポリスチレン系樹脂粒子は、下記改善の余地がある。特許文献１においては、発泡性ポリスチレン系樹脂粒子にポリエーテル及びシリカを塗布しているが、最終製品である発泡成形体の融着率が低いといった課題がある。特許文献２においては、液状の脂肪酸トリグリセリド（ひまし油）を塗布しているため、予備発泡粒子表面が侵食し、連泡率（表面に穴が多数存在）が高くなり、発泡成形体の実用強度が低下する。
又、特許文献３においては、メチルフェニルポリシロキサンの塗布により、予備発泡粒子の帯電が多く、ネットホッパー等に付着して、取り扱いが困難である。
However, the expandable polystyrene resin particles described in Patent Documents 1 to 3 have room for the following improvements. In Patent Document 1, polyether and silica are applied to expandable polystyrene-based resin particles, but there is a problem that the fusion rate of the foam molded product as the final product is low. In Patent Document 2, since a liquid fatty acid triglyceride (castor oil) is applied, the surface of the pre-expanded particles is eroded, the open cell ratio (there are many holes on the surface) increases, and the practical strength of the foamed product is reduced. descend.
Further, in Patent Document 3, the pre-expanded particles are highly charged due to the application of methylphenylpolysiloxane, and adhere to a net hopper or the like, making handling difficult.
本発明の一態様は、発泡性スチレン系樹脂粒子の流動性を良好な状態に維持し、粉体の剥離、ブロッキング量を抑制しつつ、予備発泡粒子の帯電性を抑制し、良好な融着性および表面性を有する発泡成形体を得ることに適した発泡性スチレン系樹脂粒子を提供することを目的とする。 One aspect of the present invention is to maintain the fluidity of the expandable styrene resin particles in a good state, suppress the peeling of the powder and the amount of blocking, suppress the chargeability of the pre-expanded particles, and achieve good fusion. An object of the present invention is to provide expandable styrenic resin particles suitable for obtaining foamed molded articles having good properties and surface properties.
本発明者は、前記課題を解決するために鋭意検討した結果、発泡性スチレン系樹脂粒子本体の表面に、特定の液状物、適切な量の粘土鉱物、及び、融着促進剤を前記表面に塗布することにより、樹脂粒子の流動性を良好な状態に維持し、粉体の剥離を抑制しつつ、ブロッキングを防止し、さらに良好な融着性および表面性を有する発泡成形体を得ることに適した発泡性スチレン系樹脂粒子を得ることができることを確認して、本発明を完成させた。 As a result of intensive studies to solve the above problems, the present inventors have found that a specific liquid substance, an appropriate amount of clay mineral, and a fusion promoter are added to the surface of the expandable styrene resin particle main body. By coating, the fluidity of the resin particles is maintained in a good state, the detachment of the powder is suppressed, blocking is prevented, and a foam molded article having good fusion bondability and surface properties can be obtained. After confirming that suitable expandable styrene resin particles can be obtained, the present invention was completed.
すなわち本発明の一実施形態は、以下の構成を含むものである。
[１] 発泡剤を含有する発泡性スチレン系樹脂粒子であって、発泡性スチレン系樹脂粒子本体の表面に、前記発泡性スチレン系樹脂粒子１００重量部に対して、ポリエーテル及び流動パラフィンの少なくともいずれか１種を含む液状物（Ａ）が０．３重量部以下、粘土鉱物（Ｂ）が０．０１重量部以上１重量部以下、及び、融着促進剤（Ｃ）が０重量部超０．５重量部以下が塗布されてなる発泡性スチレン系樹脂粒子。
[２] 前記液状物（Ａ）は、水に難溶であるポリエーテルを含み、
前記ポリエーテルは、ポリプロピレングリコール及びポリエチレングリコールの少なくともいずれか1種を含有する、[１]に記載の発泡性スチレン系樹脂粒子。
[３] 前記粘土鉱物（Ｂ）が、平均粒径３０μm以下の、タルク、雲母、及び、カオリンよりなる群から選択される少なくともいずれか1種を含む、[１]～[２]のいずれかに記載の発泡性スチレン系樹脂粒子。
[４] 前記融着促進剤（Ｃ）が、脂肪酸モノグリセリド、脂肪酸ジグリセリド、脂肪酸トリグリセリド、及び、ヒドロキシ脂肪酸トリグリセライドよりなる群から選択される少なくとも１種を含む、[１]～[３]のいずれかに記載の発泡性スチレン系樹脂粒子。
[５] ［１］から［４］のいずれか１項に記載の発泡性ポリスチレン系樹脂粒子を予備発泡してなる予備発泡粒子。
[６]［５］に記載の予備発泡粒子を成形してなる発泡成形体。
[７]発泡剤を含有する発泡性スチレン系樹脂粒子本体を得る工程と、前記発泡性スチレン系樹脂粒子本体の表面に、前記発泡性スチレン系樹脂粒子本体１００重量部に対して、ポリエーテル及び流動パラフィンの少なくともいずれか１種を含む液状物（Ａ）を、０．３重量部以下、粘土鉱物（Ｂ）を、０．０１重量部以上１重量部以下、及び、融着促進剤（Ｃ）を、０重量部超０．５重量以下、塗布する塗布工程と、を含む発泡性スチレン系樹脂粒子の製造方法。
That is, one embodiment of the present invention includes the following configurations.
[1] Expandable styrene resin particles containing a blowing agent, wherein at least polyether and liquid paraffin are added to 100 parts by weight of the expandable styrene resin particles on the surfaces of the expandable styrene resin particles. 0.3 parts by weight or less of a liquid (A) containing any one of them, 0.01 to 1 part by weight of a clay mineral (B), and more than 0 parts by weight of a fusion promoter (C) Expandable styrene resin particles coated with 0.5 parts by weight or less.
[2] The liquid material (A) contains a polyether that is sparingly soluble in water,
The expandable styrene resin particles according to [1], wherein the polyether contains at least one of polypropylene glycol and polyethylene glycol.
[3] Any one of [1] to [2], wherein the clay mineral (B) contains at least one selected from the group consisting of talc, mica, and kaolin having an average particle size of 30 μm or less. The expandable styrene resin particles according to .
[4] Any one of [1] to [3], wherein the fusion promoter (C) contains at least one selected from the group consisting of fatty acid monoglycerides, fatty acid diglycerides, fatty acid triglycerides, and hydroxy fatty acid triglycerides. The expandable styrene resin particles according to .
[5] Pre-expanded particles obtained by pre-expanding the expandable polystyrene resin particles according to any one of [1] to [4].
[6] A foam molded article obtained by molding the pre-expanded particles according to [5].
[7] a step of obtaining expandable styrene resin particle bodies containing a blowing agent; 0.3 parts by weight or less of a liquid (A) containing at least one liquid paraffin, 0.01 to 1 part by weight of a clay mineral (B), and a fusion accelerator (C ) above 0 parts by weight and 0.5 parts by weight or less.
本発明の一態様によれば、樹脂粒子の流動性を良好な状態に維持し、粉体の剥離を抑制しつつ、ブロッキングを防止し、さらに良好な融着性および表面性を有する発泡成形体を得ることに適した発泡性ポリスチレン系樹脂粒子を得ることができる。また、発泡性ポリスチレン系樹脂粒子を予備発泡させてなるポリスチレン系予備発泡粒子、並びに、ポリスチレン系予備発泡粒子を成形してなる発泡成形体は、発泡性ポリスチレン系樹脂粒子から粉体が剥離することが抑制されるので、その生産性が向上される。 According to one aspect of the present invention, a foam molded article that maintains good fluidity of resin particles, prevents blocking while suppressing peeling of powder, and has good fusion bondability and surface properties. It is possible to obtain expandable polystyrene resin particles suitable for obtaining In addition, the polystyrene pre-expanded particles obtained by pre-expanding the expandable polystyrene resin particles, and the expansion molded product obtained by molding the polystyrene pre-expanded particles are subject to the problem that the powder is peeled off from the expandable polystyrene resin particles. is suppressed, the productivity is improved.
本発明の一実施形態について以下に説明するが、本発明はこれに限定されるものではない。本発明は、以下に説明する各構成に限定されるものではなく、請求の範囲に示した範囲で種々の変更が可能である。また、異なる実施形態または実施例にそれぞれ開示された技術的手段を適宜組み合わせて得られる実施形態または実施例についても、本発明の技術的範囲に含まれる。さらに、各実施形態にそれぞれ開示された技術的手段を組み合わせることにより、新しい技術的特徴を形成することができる。なお、本明細書中に記載された学術文献および特許文献の全てが、本明細書中において参考文献として援用される。また、本明細書において特記しない限り、数値範囲を表す「Ａ～Ｂ」は、「Ａ以上（Ａを含みかつＡより大きい）Ｂ以下（Ｂを含みかつＢより小さい）」を意図する。 An embodiment of the invention will be described below, but the invention is not limited thereto. The present invention is not limited to each configuration described below, and various modifications are possible within the scope of the claims. Further, embodiments or examples obtained by appropriately combining technical means disclosed in different embodiments or examples are also included in the technical scope of the present invention. Furthermore, new technical features can be formed by combining the technical means disclosed in each embodiment. In addition, all the scientific literatures and patent documents described in this specification are used as references in this specification. In addition, unless otherwise specified in this specification, "A to B" representing a numerical range means "A or more (including A and greater than A) and B or less (including B and less than B)".
本明細書においては、発泡性スチレン系樹脂粒子そのもの（それ自体）を「発泡性スチレン系樹脂粒子本体」と称し、発泡性スチレン系樹脂粒子本体の表面に、外添剤（帯電防止剤、融着阻害剤）等が塗布されたものを「発泡性スチレン系樹脂粒子」と称し、発泡性スチレン系樹脂粒子を予備発泡（一次発泡）させてなる粒子を「予備発泡粒子」と称する。 In this specification, the expandable styrene resin particles themselves (per se) are referred to as "expandable styrene resin particle bodies", and external additives (antistatic agent, melting agent, etc.) are added to the surfaces of the expandable styrene resin particle bodies. The particles coated with the adhesion inhibitor) are referred to as "expandable styrene resin particles", and the particles obtained by pre-expanding (primary expansion) the expandable styrene resin particles are referred to as "pre-expanded particles".
〔１．発泡性スチレン系樹脂粒子〕
〔本発明の一実施形態の概要〕
本発明の一実施形態は、発泡性スチレン系樹脂粒子本体の表面に、前記発泡性スチレン系樹脂粒子１００重量部に対して、ポリエーテル及び流動パラフィンの少なくともいずれか１種を含む液状物Ａが０．３重量部以下、粘土鉱物Ｂが０．０１重量部１重量部以下、融着促進剤Ｃが０重量部超０．５重量部以下が塗布してなる発泡性スチレン系樹脂粒子である。
[1. Expandable styrene resin particles]
[Outline of one embodiment of the present invention]
In one embodiment of the present invention, a liquid material A containing at least one of polyether and liquid paraffin is applied to the surfaces of the expandable styrene resin particles, based on 100 parts by weight of the expandable styrene resin particles. Expandable styrene-based resin particles coated with 0.3 parts by weight or less, 0.01 parts by weight or less of clay mineral B, 1 part by weight or less, and more than 0 parts by weight and 0.5 parts by weight or less of fusion accelerator C. .
〔発泡性スチレン系樹脂粒子本体〕
発泡性スチレン系樹脂粒子本体は、基材樹脂及び発泡剤、必要に応じて添加剤を含む発泡性樹脂からなる粒子である。
[Body of expandable styrene resin particles]
The expandable styrene-based resin particle body is a particle made of an expandable resin containing a base resin, a blowing agent, and, if necessary, an additive.
（基材樹脂）
本明細書における基材樹脂は、スチレン系樹脂があげられ、適宜添加剤とのブレンドで、押出機による溶融混錬による樹脂粒子や、又、耐圧容器によるスチレン系単量体を、水系懸濁重合法やシード重合法で重合した樹脂粒子でも構わない。
単量体を重合法で製造するスチレン系樹脂としては、スチレンの単独重合体、スチレン単量体と、スチレン単量体以外の単量体との共重合体であってもよい。スチレン単量体以外の単量体としては、エチレン、ブタジエン、アクリロニトリル、スチレン系誘導体、アクリル酸エステル等が挙げられる。上記スチレン系誘導体としては、α－メチルスチレン、パラメチルスチレン、ｔ－ブチルスチレンおよびクロルスチレン等が挙げられる。上記アクリル酸エステルとしては、アクリル酸メチル、アクリル酸ブチル等のアクリル酸アルキルエステルが挙げられる。これらのスチレン単量体以外の単量体は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
(Base resin)
The base resin in this specification includes styrene-based resins, which are appropriately blended with additives, resin particles obtained by melt-kneading using an extruder, or styrene-based monomers obtained by using a pressure-resistant vessel, and suspended in an aqueous system. Resin particles polymerized by a polymerization method or a seed polymerization method may also be used.
Styrene-based resins produced by polymerizing monomers may be styrene homopolymers or copolymers of styrene monomers and monomers other than styrene monomers. Examples of monomers other than styrene monomers include ethylene, butadiene, acrylonitrile, styrene derivatives, acrylic acid esters, and the like. Examples of the styrene derivatives include α-methylstyrene, paramethylstyrene, t-butylstyrene and chlorostyrene. Examples of the acrylic acid ester include acrylic acid alkyl esters such as methyl acrylate and butyl acrylate. These monomers other than styrene monomers may be used singly or in combination of two or more.
（発泡剤）
発泡剤を樹脂粒子に含浸する方法は、押出機で溶融混錬した樹脂中に発泡剤を圧入する方法（クエンチ法）や、押出機で得られた樹脂粒子を、耐圧容器内で樹脂融点より低い温度で、発泡剤を含浸する方法（ミニペレ後含浸法）等の、公知の方法が知られている。一方、重合法で製造する場合は、耐圧容器内で、重合後の樹脂粒子に発泡剤を含浸する等の、公知の方法が知られている。
(foaming agent)
The method of impregnating the resin particles with the foaming agent includes a method of injecting the foaming agent into the resin melted and kneaded by an extruder (quenching method), and the resin particles obtained by the extruder are placed in a pressure vessel above the melting point of the resin. Known methods are known, such as the method of impregnating with a blowing agent at low temperatures (post-mini-pellet impregnation method). On the other hand, in the case of production by a polymerization method, a known method is known, such as impregnating the polymerized resin particles with a foaming agent in a pressure vessel.
発泡剤としては、プロパン、ブタン、ペンタン等の脂肪族炭化水素；シクロブタン、シクロペンタン等の脂環族炭化水素；メチルクロライド、ジクロロジフルオロメタン、ジクロロテトラフルオロエタン等のハロゲン化炭化水素；等が挙げられる。その中でも、発泡力が良好である点から、ブタンがより好ましい。これら発泡剤は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Examples of blowing agents include aliphatic hydrocarbons such as propane, butane and pentane; alicyclic hydrocarbons such as cyclobutane and cyclopentane; halogenated hydrocarbons such as methyl chloride, dichlorodifluoromethane and dichlorotetrafluoroethane; be done. Among them, butane is more preferable because of its good foaming power. These foaming agents may be used individually by 1 type, and may be used in combination of 2 or more type.
発泡性スチレン系樹脂粒子本体における発泡剤の含有量は、最終製品である発泡成形体の所望する倍率で適時選定されるが、発泡性スチレン系樹脂粒子本体１００重量部に対し、３．０重量部以上であることが好ましく、３．５重量部以上であることがより好ましく、また、７．０重量部以下であることが好ましく、５．０重量部以下であることがより好ましい。発泡剤の含有量が上記範囲であれば、予備発泡工程において加熱時間が長くなることを防ぎ、ブロッキングを抑制すると共に、発泡成形体の製造にかかる時間を短縮し、成形工程の成形サイクルを短くすることができる。 The content of the foaming agent in the main body of the expandable styrene resin particles is appropriately selected according to the desired magnification ratio of the foamed molded product, which is the final product. parts by weight or more, more preferably 3.5 parts by weight or more, and preferably 7.0 parts by weight or less, more preferably 5.0 parts by weight or less. If the content of the foaming agent is within the above range, it is possible to prevent the heating time from becoming long in the preliminary foaming step, suppress blocking, shorten the time required to produce the foam molded product, and shorten the molding cycle of the molding step. can do.
（添加剤）
基材樹脂に適宜添加する添加剤としては、溶剤、可塑剤、造核剤、難燃剤、難燃助剤等が挙げられる。
(Additive)
Additives that are appropriately added to the base resin include solvents, plasticizers, nucleating agents, flame retardants, and auxiliary flame retardants.
溶剤および可塑剤の具体例としては、へキサン、ヘプタン等の炭素数６以上の脂肪族炭化水素；シクロヘキサン、シクロオクタン等の炭素数６以上の脂環族炭化水素、ジイソブチルアジペート、ジオクチルアジペート、ジブチルセバケート、グリセリントリステアレート、グリセリントリカプリレート、ヤシ油、パーム油、菜種油；等が挙げられる。
造核剤の具体例としては、メタクリル酸メチル系共重合体、ポリエチレンワックス、タルク、脂肪酸ビスアマイド、エチレン－酢酸ビニル共重合体等が挙げられる。脂肪酸ビスアマイドの具体例としては、例えば、メチレンビスステアリルアマイド、エチレンビスステアリルアマイド、ヘキサメチレンビスパルミチン酸アマイド、エチレンビスオレイン酸アマイド等が挙げられる。
Specific examples of solvents and plasticizers include aliphatic hydrocarbons having 6 or more carbon atoms such as hexane and heptane; alicyclic hydrocarbons having 6 or more carbon atoms such as cyclohexane and cyclooctane; sebacate, glycerin tristearate, glycerin tricaprylate, coconut oil, palm oil, rapeseed oil;
Specific examples of nucleating agents include methyl methacrylate copolymers, polyethylene wax, talc, fatty acid bisamides, ethylene-vinyl acetate copolymers, and the like. Specific examples of fatty acid bisamides include methylenebisstearylamide, ethylenebisstearylamide, hexamethylenebispalmitamide, and ethylenebisoleamide.
難燃剤としては、公知の難燃剤を使用することができる。具体例としては、ヘキサブロモシクロドデカン、テトラブロモブタン、ヘキサブロモシクロヘキサン等のハロゲン化脂肪族炭化水素系化合物；テトラブロモビスフェノールＡ、テトラブロモビスフェノールＦ、２，４，６－トリブロモフェノール等の臭素化フェノール類；テトラブロモビスフェノールＡ－ビス（２，３－ジブロモプロピルエーテル）、テトラブロモビスフェノールＡ－ビス（２，３－ジブロモ－２－メチルプロピルエーテル）、テトラブロモビスフェノールＡ－ジグリシジルエーテル、２，２－ビス［４’－（２”，３”－ジブロモアルコキシ）－３’，５’－ジブロモフェニル］－プロパン等の臭素化フェノール誘導体；臭素化スチレン－ブタジエンブロック共重合体、臭素化ランダムスチレン－ブタジエン共重合体、臭素化スチレン－ブタジエングラフト共重合体等の臭素化ブタジエン－ビニル芳香族炭化水素共重合体（例えば、Chemtura社製のEMERALD3000、若しくは、特表２００９－５１６０１９号公報に記載されている共重合体）；等が挙げられる。
難燃助剤としては、公知の難燃助剤を使用することができる。具体例としては、クメンハイドロパーオキサイド、ジクミルパーオキサイド、ｔ－ブチルハイドロパーオキサイド、２，３－ジメチル－２，３－ジフェニルブタン等が挙げられる。
A known flame retardant can be used as the flame retardant. Specific examples include halogenated aliphatic hydrocarbon compounds such as hexabromocyclododecane, tetrabromobutane, and hexabromocyclohexane; bromine compounds such as tetrabromobisphenol A, tetrabromobisphenol F, and 2,4,6-tribromophenol phenols; tetrabromobisphenol A-bis(2,3-dibromopropyl ether), tetrabromobisphenol A-bis(2,3-dibromo-2-methylpropyl ether), tetrabromobisphenol A-diglycidyl ether, 2 ,2-bis[4′-(2″,3″-dibromoalkoxy)-3′,5′-dibromophenyl]-propane and other brominated phenol derivatives; brominated styrene-butadiene block copolymers, brominated random Brominated butadiene copolymers such as styrene-butadiene copolymers and brominated styrene-butadiene graft copolymers-vinyl aromatic hydrocarbon copolymers (for example, EMERALD3000 manufactured by Chemtura Co., or described in JP-T-2009-516019) copolymer); and the like.
Known flame retardant aids can be used as the flame retardant aid. Specific examples include cumene hydroperoxide, dicumyl peroxide, t-butyl hydroperoxide, 2,3-dimethyl-2,3-diphenylbutane and the like.
これら添加剤は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
又、上記の発泡性スチレン系樹脂粒子本体に、非イオン界面活性剤を塗布、乾燥することにより、樹脂粒子表面にクラック構造を形成した発泡性スチレン系樹脂粒子本体を用いても構わない。クラック構造を形成することによって、液状物Ａの添付力が増大する傾向がある。液状物非イオン界面活性剤の具体例としては、ポリオキシエチレンセチルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンラウレート、ポリオキシエチレンパルミテート、ポリオキシエチレンステアレート、ポリオキシエチレンオレエート等が挙げられる。これら非イオン界面活性剤は、１種を用いてもよく、２種以上を組み合わせて用いてもよい。
These additives may be used singly or in combination of two or more.
Alternatively, an expandable styrene resin particle body may be used in which a crack structure is formed on the resin particle surface by applying a nonionic surfactant to the above expandable styrene resin particle body and drying. Forming a crack structure tends to increase the attachment force of the liquid A. As shown in FIG. Specific examples of liquid nonionic surfactants include polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene palmitate, polyoxyethylene stearate, poly oxyethylene oleate and the like. These nonionic surfactants may be used alone or in combination of two or more.
〔発泡性スチレン系樹脂粒子本体の体積平均粒子径〕
本発明の発泡性スチレン系樹脂粒子本体の体積平均粒子径は、発泡性スチレン系樹脂粒子本体の平均粒子径ともいえる。本発泡性スチレン系樹脂粒子の体積平均粒子径は、発泡成形体の用途等に応じて適宜に設定することができるが、一般に、懸濁重合法で製造された樹脂粒子の体積平均粒子径は、０．５ｍｍ以上１．２ｍｍ以下であり、シ－ド重合法で製造された粒子径は、０．２ｍｍ以上０．５ｍｍ以下である。又、押出機によるクエンチ法で製造された粒子径は、１．０ｍｍ以上１．５ｍｍ以下である。本願明細書において、発泡性スチレン系樹脂粒子本体の体積平均粒子径は、画像処理方式マイクロトラックＪＰＡを使用して測定される値である。
[Volume average particle diameter of expandable styrene resin particle body]
The volume average particle size of the expandable styrene resin particle main body of the present invention can also be said to be the average particle size of the expandable styrene resin particle main body. The volume-average particle diameter of the present expandable styrene-based resin particles can be appropriately set according to the application of the foam molded product, etc., but generally the volume-average particle diameter of the resin particles produced by the suspension polymerization method is , 0.5 mm or more and 1.2 mm or less, and the particle diameter produced by the seed polymerization method is 0.2 mm or more and 0.5 mm or less. Moreover, the particle diameter produced by the quenching method using an extruder is 1.0 mm or more and 1.5 mm or less. In the specification of the present application, the volume average particle diameter of the expandable styrene-based resin particle main body is a value measured using an image processing system Microtrac JPA.
〔発泡性スチレン系樹脂粒子〕
本発明の発泡性スチレン系樹脂粒子は、発泡性スチレン系樹脂粒子本体の製造により得られたものである。上記〔発泡性スチレン系樹脂粒子本体〕にて述べた通り、発泡性スチレン系樹脂粒子本体を得る工程は特に限定されず、クエンチ法に採用される工程、ミニペレ後含浸法に採用される工程及び重合法に採用される工程等の公知の工程が含まれる。
[Expandable styrene resin particles]
The expandable styrene resin particles of the present invention are obtained by manufacturing the expandable styrene resin particle bodies. As described in [Main body of expandable styrene resin particles] above, the process for obtaining the main body of expandable styrene resin particles is not particularly limited. Known steps such as those employed in polymerization processes are included.
〔発泡性スチレン系樹脂粒子の製造〕
本発明の発泡性スチレン系樹脂粒子は、前記発泡性スチレン系樹脂粒子本体の表面に、前記発泡性スチレン系樹脂粒子本体１００重量部に対して、ポリエーテル及び流動パラフィンの少なくともいずれか１種を含む液状物Ａを、０．３重量部以下、粘土鉱物Ｂを０．０１重量部以上１重量部以下、及び、融着促進剤Ｃを０重量部超０．５重量以下塗布する塗布工程とすることにより、製造することができる。
[Production of expandable styrene resin particles]
In the expandable styrene resin particles of the present invention, at least one of polyether and liquid paraffin is added to 100 parts by weight of the expandable styrene resin particle main body on the surface of the expandable styrene resin particle main body. a coating step of applying 0.3 parts by weight or less of a liquid A containing, 0.01 to 1 part by weight of a clay mineral B, and more than 0 parts by weight and 0.5 parts by weight or less of a fusion promoter C; It can be manufactured by
発泡性スチレン系樹脂粒子本体の表面に対して液状物Ａが塗布される場合には、液状物Ａが塗布された後に、粘土鉱物Ｂ、及び、融着促進剤Ｃが塗布されることが好ましい。なお、粘土鉱物Ｂ及び融着促進剤Ｃは同時に塗布されてもよく、それぞれ別々に塗布されてもよい。以下では、本発明の一実施形態として、液状物Ａ、粘土鉱物Ｂ、及び、融着促進剤Ｃを、発泡性スチレン系樹脂粒子本体の表面に塗布した発泡性ポリスチレン系樹脂粒子の製造方法であって、液状物Ａが塗布された後に、粘土鉱物Ｂ、及び、融着促進剤Ｃが塗布される態様を説明する。また、以下では、説明の便宜上、液状物Ａを塗布する工程を第１塗布工程と称し、粘土鉱物Ｂ、及び、融着促進剤Ｃを塗布する工程を第２工程と称する。 When the liquid material A is applied to the surface of the expandable styrene resin particle body, it is preferable that the clay mineral B and the fusion promoter C are applied after the liquid material A is applied. . The clay mineral B and the fusion promoter C may be applied simultaneously or separately. In the following, as an embodiment of the present invention, a method for producing expandable polystyrene resin particles in which a liquid A, a clay mineral B, and a fusion promoter C are applied to the surface of the expandable styrene resin particles main body. A description will now be given of a mode in which the clay mineral B and the fusion promoter C are applied after the liquid material A is applied. Further, hereinafter, for convenience of explanation, the step of applying the liquid material A will be referred to as the first application step, and the step of applying the clay mineral B and the fusion promoter C will be referred to as the second step.
（第１塗布工程）
第１塗布工程は、発泡性スチレン系樹脂粒子本体の表面に、ポリエーテル及び流動パラフィンの少なくともいずれか１種を含む液状物Ａを塗布する工程である。ポリエーテル及び流動パラフィンは、いずれも、常温（２５℃）で水に難溶である。
ポリエーテルは、アルキレンオキシドからの誘導体であり、具体的に、ポリプロピレングリコール、ポリオキシプロピレン－グリコールエーテル、ポリオキシプロピレン－ジグリセリエーテル、ポリプロピレン－ジグリコール・シルビトールエーテル、ポリブチレングリコール、ポリエチレングリコール・ポリプロピレン・ペンタエリスリトールエーテル、ポリエチレングリコール等々が挙げられる。特に、好ましくは、ポリプロピレングリコール、ポリエチレングリコールが、安価であり、かつ、取り扱いやすい。
(First coating step)
The first application step is a step of applying a liquid material A containing at least one of polyether and liquid paraffin to the surfaces of the expandable styrene resin particles. Both polyether and liquid paraffin are sparingly soluble in water at room temperature (25°C).
Polyethers are derivatives from alkylene oxides, specifically polypropylene glycol, polyoxypropylene-glycol ether, polyoxypropylene-diglyceryl ether, polypropylene-diglycol silbitol ether, polybutylene glycol, polyethylene glycol-ether. polypropylene-pentaerythritol ether, polyethylene glycol, and the like. Polypropylene glycol and polyethylene glycol are particularly preferable because they are inexpensive and easy to handle.
流動パラフィンの具体例としては、炭素数１５～３５の飽和炭化水素が挙げられる。 Specific examples of liquid paraffin include saturated hydrocarbons having 15 to 35 carbon atoms.
液状物Ａは、発泡性スチレン系樹脂粒子の表面を侵食し難い物質であることが好ましい。スチレン系樹脂のＳＰ値（溶解度パラメータ）８であるから、離れたＳＰ値をもつ物質が好適であり、例えば、ポリエーテル及び流動パラフィンのＳＰ値は、各々１０、１６であり、発泡性スチレン系樹脂粒子の表面を侵食し難く、予備発泡粒子の連泡率の増加を抑制し、最終製品の機械的強度の低下が少ない。流動パラフィンのように、ＳＰ値が大きくかけ離れると、スチレン系樹脂粒子の添着性が少なくなる傾向であるため、液状物Ａとしては、ポリエーテルが特に好ましい。 The liquid A is preferably a substance that hardly corrodes the surface of the expandable styrene resin particles. Since the SP value (solubility parameter) of styrenic resin is 8, substances with separate SP values are suitable, for example, the SP values of polyether and liquid paraffin are 10 and 16, respectively, It hardly corrodes the surface of resin particles, suppresses an increase in the open cell ratio of pre-expanded particles, and reduces the mechanical strength of the final product. As in liquid paraffin, when the SP value is greatly different, the adherence of the styrene-based resin particles tends to decrease. Therefore, as the liquid A, polyether is particularly preferable.
液状物Ａは水に難溶であることが重要で、予備発泡工程、成形工程で、使用される加熱水蒸気による液状物Ａの溶解等が生じにくいため、第２塗布工程で塗布する粘土鉱物Ｂ、融着促進剤Ｃが剥がれることを防止することができる。例えば、分子量１０００以上のポリプロピレングリコールは、水に難溶である。
又、液状物Ａの動粘度（２５℃）は、１００ｍｍ２／Ｓ以上５００ｍｍ２／Ｓ以下の範囲が好ましく、１００ｍｍ２／Ｓ未満であると、樹脂粒子本体から流れてしまう傾向があり、５００ｍｍ２／Ｓを超えると、樹脂粒子との混合に長時間を要する傾向である。
It is important that the liquid A is sparingly soluble in water, and in the pre-foaming process and the molding process, the heated steam used does not easily dissolve the liquid A, so the clay mineral B applied in the second coating process , the fusion accelerator C can be prevented from peeling off. For example, polypropylene glycol with a molecular weight of 1000 or more is sparingly soluble in water.
In addition, the kinematic viscosity (25° C.) of the liquid A is preferably in the range of 100 mm 2 /S or more and 500 mm 2 /S or less. If it exceeds 2 /S, it tends to take a long time to mix with the resin particles.
液状物Ａの塗布量は、発泡性スチレン系樹脂粒子本体１００重量部に対して、０．３重量以下（０重量部を含む）であることがより好ましく、０．２５重量部以下であり、０．２重量部以下であることがより好ましい。また、
液状物Ａは塗布されていなくてもよく、液状物Ａが塗布される場合には、発泡性スチレン系樹脂粒子本体１００重量部に対して、０重量部以上であることが好ましく、０．０１重量部以上であることがより好ましく、０．０２重量部以上であることが更に好ましい。
The amount of liquid A to be applied is more preferably 0.3 parts by weight or less (including 0 parts by weight), more preferably 0.25 parts by weight or less, with respect to 100 parts by weight of the expandable styrene resin particles. It is more preferably 0.2 parts by weight or less. again,
The liquid A may not be applied, and when the liquid A is applied, it is preferably 0 parts by weight or more with respect to 100 parts by weight of the expandable styrene resin particle main body, and 0.01. It is more preferably at least 0.02 part by weight, and even more preferably at least 0.02 part by weight.
液状物Ａの塗布量が上記範囲であれば、樹脂粒子本体との均一混合ができ、樹脂粒子の流動性が良好で、取り扱いが容易である。液状物Ａが０重量部の場合、第２塗布工程で塗布する粘土鉱物Ｂ、融着促進剤Ｃが容易に剥がれてしまう傾向はあるものの、正帯電する粘土鉱物Ｂと負帯電するポリスチレン系樹脂との静電吸引で、粉はく離は抑制される。塗布量が０．３重量部を超えると、樹脂粒子の流動性（安息角）が悪化し、予発時のブロッキングが増加する。 If the coating amount of the liquid substance A is within the above range, it can be uniformly mixed with the main body of the resin particles, the fluidity of the resin particles is good, and the handling is easy. When the liquid material A is 0 parts by weight, the clay mineral B and the fusion promoter C applied in the second coating process tend to be easily peeled off, but the positively charged clay mineral B and the negatively charged polystyrene resin. Powder flaking is suppressed by electrostatic attraction with When the coating amount exceeds 0.3 parts by weight, the fluidity (angle of repose) of the resin particles deteriorates, and blocking at the time of occurrence increases.
（第２塗布工程）
第２塗布工程は、前記第1塗布工程後に実施する工程であって、発泡性スチレン系樹脂粒子本体の表面に、粘土鉱物Ｂ及び融着促進剤Ｃを塗布する工程である。
粘土鉱物Ｂとは、具体的にはケイ酸塩鉱物であり、帯電列表の正帯電に位置する物質が好ましい。粘土鉱物Ｂが正帯電する物質であることで、負帯電するポリスチレン系樹脂粒子本体と静電吸引し、剥がれ難くなるためである。一方、負帯電するケイ酸塩鉱物ではないシリカ（ＳｉＯ２）や一般的にブロッキング防止剤として使用される脂肪酸金属塩（ステアリン酸亜鉛）は、ポリスチレン系樹脂粒子本体と静電反発するために、剥がれ易い傾向にある。
(Second coating step)
The second application step is a step that is performed after the first application step, and is a step of applying the clay mineral B and the fusion promoter C to the surface of the expandable styrene-based resin particle main body.
The clay mineral B is specifically a silicate mineral, preferably a positively charged substance in the electrification chart. This is because the clay mineral B, which is a positively charged substance, is electrostatically attracted to the negatively charged polystyrene-based resin particle main body, making it difficult to separate. On the other hand, silica (SiO2), which is not a negatively charged silicate mineral, and fatty acid metal salt (zinc stearate), which is generally used as an antiblocking agent, cause electrostatic repulsion with the main body of polystyrene resin particles. tend to be easy.
また、発明者らは、発泡性スチレン系樹脂粒子本体の表面に粘土鉱物Ｂを塗布することで、発泡性スチレン系樹脂粒子を発泡させた予備発泡粒子の帯電が抑制されることを新たに見出した。ここで、予備発泡粒子が帯電していると、ネットホッパー等に付着して取り扱いが困難であるだけでなく、予備発泡粒子は、空気輸送により運搬若しくは乾燥しつつ配管内を移動するところ、スチレン系樹脂を含む予備発泡粒子は電気絶縁性が高いために、摩擦によって帯電しやすい特徴を持つ。このため、帯電に由来する静電気の放電により、発泡剤としての炭化水素に着火、爆発する可能性がある。本発明においては、発泡性スチレン系樹脂粒子本体の表面に粘土鉱物Ｂが塗布されていることで、ブロッキングが抑制されるだけでなく、予備発泡粒子の帯電を抑制することができる。
粘土鉱物Ｂの具体例として、平均粒径３０μm以下、好ましくは２０μｍ以下、 １μｍ以上の粉状の、カオリナイト、雲母、タルク、ゼオライト、クロライト、グローコナイト、スメクタイト等のケイ酸塩鉱物が挙げられ、更に好ましくは、安価で容易に入手可能なカオリナイト、雲母、タルクである。これらの粘土鉱物は単独で用いても良いし、２種以上を混合しても良い。
In addition, the inventors have newly found that the charging of pre-expanded particles obtained by expanding the expandable styrene resin particles is suppressed by applying the clay mineral B to the surface of the expandable styrene resin particles. rice field. Here, if the pre-expanded particles are electrically charged, they not only adhere to a net hopper or the like and are difficult to handle. Since the pre-expanded particles containing the base resin have high electrical insulation, they are characterized by being easily electrified by friction. For this reason, there is a possibility that the hydrocarbon used as the foaming agent will ignite and explode due to the discharge of static electricity derived from charging. In the present invention, the clay mineral B is applied to the surface of the expandable styrene-based resin particle main body, so that not only blocking can be suppressed, but also charging of the pre-expanded particles can be suppressed.
Specific examples of the clay mineral B include powdery silicate minerals such as kaolinite, mica, talc, zeolite, chlorite, glauconite, and smectite having an average particle size of 30 μm or less, preferably 20 μm or less, or 1 μm or more. Kaolinite, mica, and talc, which are inexpensive and readily available, are more preferred. These clay minerals may be used alone or in combination of two or more.
粘土鉱物Ｂの平均粒径が、上記範囲であれば、予発発泡時のブロッキングが抑制することができるが、平均粒径３０μｍを超えると、樹脂粒子本体表面の粘土鉱物Ｂの被覆率が小さくなり、ブロッキング量が増加する傾向であり、１μｍ未満であれば、被覆率が増加し、ブロッキング量は減少するものの、発泡成形体の強度が低下する傾向がある。
粘土鉱物Ｂの塗布量は、発泡性スチレン系樹脂粒子本体１００重量部に対して、０．０１重量部以上１重量部以下であり、０．０５重量以上０．６重量部以下が好ましく、０．０５重量部以上０．４重量部以上がより好ましい。
粘土鉱物Ｂの添加量が上記範囲であれば、予備発泡時のブロッキング及び、予備発泡粒子の帯電性を抑制し、容易に割れない実用強度のある発泡成形体が得られる。粘土鉱物Ｂは融着阻害物質として働くため、０．６重量部を超えると、発泡成形体が容易にわれてしまう。０．０１部未満であれば、ブロッキングが増加すると共に、得られる予備発泡粒子の帯電してしまうため貯槽ホッパー壁面に付着し、取り扱いが困難である。
If the average particle size of the clay mineral B is within the above range, blocking during pre-foaming can be suppressed. If the thickness is less than 1 μm, the coverage increases and the blocking amount decreases, but the strength of the foamed product tends to decrease.
The amount of the clay mineral B to be applied is 0.01 to 1 part by weight, preferably 0.05 to 0.6 part by weight, based on 100 parts by weight of the expandable styrene resin particles. 0.05 parts by weight or more and 0.4 parts by weight or more is more preferable.
If the amount of clay mineral B added is within the above range, blocking during pre-expansion and electrification of the pre-expanded particles are suppressed, and a non-crackable and practically strong expansion molded product can be obtained. Since the clay mineral B acts as a fusion inhibitor, if it exceeds 0.6 parts by weight, the foamed molded product will easily crack. If the amount is less than 0.01 part, blocking will increase and the pre-expanded particles obtained will be charged and adhere to the wall surface of the storage tank hopper, making handling difficult.
融着促進剤Ｃとしては、常温（２５℃）で、粉状の、融点上限１２０℃以下、より好ましくは１００℃以下の脂肪酸グリセリドが挙げられる。融点上限の１２０℃を超えると、成形加工時に融着せず、融着促進効果を損なう傾向がある。
具体的には、ラウリン酸トリグリセライド、ステアリン酸トリグリセライド、リノール酸トリグリセライド、ヒドロキシステアリン酸トリグリセライドなどの脂肪酸トリグリセライド；ラウリン酸ジグリセライド、ステアリン酸ジグリセライド、リノール酸ジグリセライドなどの脂肪酸ジグリセライド；ラウリン酸モノグリセライド、ステアリン酸モノグリセライド、リノール酸モノグリセライドなどの脂肪酸モノグリセライド；ヒマシ硬化油（ヒドロキシステアリン酸トリグリセライド）などの植物油（ヒドロキシ脂肪酸トリグリセライド）などが挙げられ、これら脂肪酸グリセリドは単独で用いても良いし、２種以上を混合しても良い。中でも、ヒマシ硬化油（融点８４℃）は、ポリスチレン系樹脂粒子表面の侵食を抑制し、発泡成形体の融着を促進するために好適である。
Examples of the fusion promoter C include powdery fatty acid glycerides having an upper melting point of 120° C. or less, more preferably 100° C. or less at room temperature (25° C.). If the upper limit of the melting point of 120°C is exceeded, fusion does not occur during molding and there is a tendency to impair the effect of promoting fusion.
Specifically, fatty acid triglycerides such as lauric acid triglyceride, stearic acid triglyceride, linoleic acid triglyceride, and hydroxystearic acid triglyceride; fatty acid diglycerides such as lauric acid diglyceride, stearic acid diglyceride, and linoleic acid diglyceride; Fatty acid monoglycerides such as linoleic acid monoglyceride; vegetable oils (hydroxy fatty acid triglycerides) such as castor hydrogenated oil (hydroxy stearic acid triglyceride); good. Among them, castor hardened oil (melting point 84° C.) is suitable for suppressing erosion of the surface of the polystyrene resin particles and promoting fusion of the foam molded product.
融着促進剤Ｃの塗布量は、発泡性スチレン系樹脂粒子本体１００重量部に対して、０重量部超０．５重量以下であり、０重量以上０．１重量部以下がより好ましく、０．５重量以上０．４重量部以下がより好ましい。融着促進剤の添加量が上記範囲であれば、予備発泡時にブロッキングを抑制できると共に、発泡成形体の実用強度を発現する。融着促進剤０．５重量部を超えると、予発時のブロッキング量が増加し、予発粒子の表面膜の破泡を促進する。 The amount of the fusion promoter C to be applied is more than 0 parts by weight and 0.5 parts by weight or less, more preferably 0 parts by weight or more and 0.1 parts by weight or less, with respect to 100 parts by weight of the expandable styrene resin particles. 0.5 parts by weight or more and 0.4 parts by weight or less is more preferable. When the amount of the fusion promoter added is within the above range, blocking can be suppressed during prefoaming, and practical strength of the foam molded product can be obtained. If the amount of the fusion promoter exceeds 0.5 parts by weight, the amount of blocking at the time of preheating increases, promoting breakage of the surface film of the preheating particles.
第２塗布工程で使用する、粘土鉱物Ｂ、及び、融着促進剤Ｃは、水に難溶の粉状物質であることが好ましい。これにより、予備発泡工程、成形工程で、使用される加熱水蒸気による、溶解、剥がれを防止することができる。
本発明の発泡性スチレン系樹脂粒子の製造の第１塗布工程及び／又は第２塗布工程において、求められる性能に応じて更なる添付剤が発泡性スチレン系樹脂粒子本体の表面に塗布されてもよい。さらに、発明の発泡性スチレン系樹脂粒子の製造方法は、第１塗布工程及び第２塗布工程以外にも、求められる性能に応じて更なる塗布工程を備えていてもよい。なお、第１塗布工程の液状物Ａを塗布した後に、第２塗布工程の粉状の粘土鉱物Ｂ、融着促進剤Ｃを塗布されることが、発泡性スチレン系樹脂粒子本体表面に塗布する剤（添付剤）をより均一に塗布することができる。
The clay mineral B and the fusion promoter C used in the second coating step are preferably powdery substances that are poorly soluble in water. This makes it possible to prevent dissolution and peeling due to the heated steam used in the pre-foaming process and the molding process.
In the first coating step and/or the second coating step of the production of the expandable styrene resin particles of the present invention, additional additives may be applied to the surfaces of the expandable styrene resin particles according to the required performance. good. Furthermore, the method for producing expandable styrene-based resin particles according to the invention may include a further coating step in addition to the first coating step and the second coating step depending on the required performance. It should be noted that after applying the liquid material A in the first application step, the powdery clay mineral B and the fusion promoter C in the second application step can be applied to the surface of the expandable styrene resin particle main body. The agent (attachment) can be applied more uniformly.
本発明の発泡性スチレン系樹脂粒子の製造方法において、発泡性スチレン系樹脂粒子本体の表面に、液状物Ａ、粘土鉱物Ｂ及び融着促進剤Ｃを塗布する方法としては、発泡性スチレン系樹脂粒子本体と各種添付剤とを混合できればよく、種々の公知の方法を用いることができる。発泡性スチレン系樹脂粒子本体と各種添付剤とを均一に混合するためには、第１塗布工程、及び第２塗布工程において混合機器を用いることが好ましい。本発明の製造方法で用いる混合機器としては、例えば、スーパーミキサー、ナウタミキサー、ユニバーサルミキサー、プロシェアミキサー、アペックスミキサー、ヘンシェルミキサー、レーディゲーミキサー等のミキサー；リボンブレンター、タンブラー型ブレンター等のブレンター；が挙げられる。混合機器は、添加物の塗布量等を考慮して、適宜に選択され得る。 In the method for producing the expandable styrene resin particles of the present invention, the method of applying the liquid A, the clay mineral B, and the fusion promoter C to the surfaces of the expandable styrene resin particles includes: Various known methods can be used as long as the main particles and various additives can be mixed. In order to uniformly mix the expandable styrene-based resin particle main body and various additives, it is preferable to use a mixing device in the first coating step and the second coating step. Mixing equipment used in the production method of the present invention includes, for example, mixers such as Super Mixer, Nauta Mixer, Universal Mixer, Proshare Mixer, Apex Mixer, Henschel Mixer and Loedige Mixer; Ribbon Blender, Tumbler Blender and the like. Brenter; A mixing device can be appropriately selected in consideration of the coating amount of the additive and the like.
上記各工程における混合時間としては、特に限定されず、混合機器の混合能力で、適宜に調整することができる。 The mixing time in each of the above steps is not particularly limited, and can be appropriately adjusted according to the mixing capacity of the mixing equipment.
〔２．予備発泡粒子〕
本発明の一実施形態に係る予備発泡粒子は、上述した発泡性スチレン系樹脂粒子を予備発泡（一次発泡）させることによって得られる。
[2. Pre-expanded particles]
The pre-expanded particles according to one embodiment of the present invention are obtained by pre-expanding (primary expansion) the expandable styrene-based resin particles described above.
予備発泡させる方法としては、例えば、円筒形の予備発泡装置を使用し、水蒸気等の加熱媒体を用いて発泡性熱可塑性樹脂粒子を加熱して発泡させる等の、通常の方法を採用することができる。 As a method for pre-expanding, for example, a normal method can be adopted, such as using a cylindrical pre-expanding device to heat expandable thermoplastic resin particles using a heating medium such as steam to expand them. can.
予備発泡装置、および予備発泡工程の条件は、発泡性スチレン系樹脂粒子本体の基材樹脂種類、所望する予備発泡倍率等に応じて適宜に設定すればよく、特に限定されない。 The pre-expansion device and the conditions of the pre-expansion step are not particularly limited, and may be appropriately set according to the base resin type of the expandable styrene-based resin particle body, the desired pre-expansion ratio, and the like.
〔３．発泡成形体〕
本発明の一実施形態に係る発泡成形体は、上述した予備発泡粒子を加熱発泡（二次発泡）させて、成形することによって得られる。
[3. Foam molded product]
A foamed molded article according to one embodiment of the present invention is obtained by heating and foaming (secondary foaming) the above pre-expanded particles and molding them.
予備発泡粒子を加熱発泡させて、成形する方法としては、例えば、金型内に予備発泡粒子を充填し、水蒸気等の加熱媒体を吹き込んで加熱する型内発泡成形法等の、通常の方法を採用することができる。 As a method of heating and foaming the pre-expanded particles for molding, for example, a conventional method such as an in-mold foam molding method in which the pre-expanded particles are filled in a mold and heated by blowing in a heating medium such as steam is used. can be adopted.
具体的な型内発泡成形方法としては、閉鎖し得るが密閉し得ない金型内に、予備発泡粒子を充填し、加熱媒体により予備発泡粒子を加熱および融着することで型内発泡成形体とする方法が挙げられる。 As a specific in-mold foam molding method, pre-expanded particles are filled in a mold that can be closed but cannot be sealed, and the pre-expanded particles are heated and fused with a heating medium to form an in-mold foam molded product. There is a method of
加熱発泡に使用する装置、および加熱発泡の条件は、発泡性スチレン系樹脂粒子本体の組成、所望する発泡倍率等に応じて適宜に設定すればよく、特に限定されない。 The device used for thermal foaming and the conditions for thermal foaming may be appropriately set according to the composition of the expandable styrene-based resin particle main body, the desired expansion ratio, etc., and are not particularly limited.
上記発泡成形体、特に型内発泡成形体は、所望の形状の成形体を作製し易い等の利点から、例えば、食品容器等の包装材料（トレー）、魚函等の輸送用梱包材、特に、低帯電性能を必要とする家電製品や精密部品の緩衝材等には好適である。 The foam-molded article, particularly the in-mold foam-molded article, has the advantage that it is easy to produce a molded article having a desired shape. It is suitable for home electric appliances that require low electrification performance, cushioning materials for precision parts, and the like.
以下、実施例および比較例により本発明をさらに詳細に説明するが、本発明はこれら実施例に限定されるものではない。なお、「部」および「％」は、特に断りのない限り、重量基準である。 EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. "Parts" and "%" are by weight unless otherwise specified.
実施例および比較例における、発泡性スチレン系樹脂粒子、および発泡成形体の、各種測定方法並びに評価方法は、以下の通りである。 Various measurement methods and evaluation methods for the expandable styrene-based resin particles and the foam molded articles in Examples and Comparative Examples are as follows.
＜発泡性スチレン系樹脂粒子の流動性の評価＞
発泡性スチレン系樹脂粒子の流動性は、安息角測定機の評価装置を利用して、下記５段階で評価した。数値の大きい方が流動性に優れた状態であり、「３」以上を合格と判定した。
<Evaluation of fluidity of expandable styrene resin particles>
The fluidity of the expandable styrene-based resin particles was evaluated using an evaluation device such as an angle-of-repose measuring machine in the following five stages. A larger numerical value indicates a state of excellent fluidity, and "3" or higher was determined to be acceptable.
前記安息角の測定方法は、以下の方法で測定した。先ず、一面が堰になっている箱を用意し、発泡性スチレン系樹脂粒子を箱に、擦切り一杯になるように投入した。投入後、前記堰を取り外して、発泡性スチレン系樹脂粒子を自然にこぼれさせた。そして、箱に残った発泡性スチレン系樹脂粒子の角度を測定し、その角度を安息角（度）とした。 The angle of repose was measured by the following method. First, a box having a weir on one side was prepared, and the expandable styrene resin particles were put into the box so that the box was completely leveled. After charging, the weir was removed and the expandable styrene resin particles were allowed to spill naturally. Then, the angle of the expandable styrene-based resin particles remaining in the box was measured, and the angle was taken as the angle of repose (degrees).
５：安息角が２５度以下で、流動性が良く、樹脂粒子がよく転がる状態
４：安息角が２５度を超え、３０度以下で、樹脂粒子が転がるが、流れが遅い状態
３：安息角が３０度を超え、３５度以下で、流動性が良く、樹脂粒子が転がるものの、斜面の一部に凹凸が残る状態
２：安息角が３５度を超え、４０度以下で、流動性は良いものの、樹脂粒子を転がすためにバイブレーターが必要な状態
１：安息角が４０度を超え、流動性が非常に悪く、樹脂粒子が転がらない状態。
安息角が３５度以下を合格とした。
5: The angle of repose is 25 degrees or less, the fluidity is good, and the resin particles roll well. 4: The angle of repose is more than 25 degrees and 30 degrees or less, and the resin particles roll, but the flow is slow. 3: The angle of repose. is over 30 degrees and 35 degrees or less, the fluidity is good, and although the resin particles roll, unevenness remains on part of the slope 2: The repose angle is over 35 degrees and 40 degrees or less, and the fluidity is good. However, a state in which a vibrator is required to roll the resin particles 1: A state in which the angle of repose exceeds 40 degrees and the fluidity is extremely poor, and the resin particles do not roll.
An angle of repose of 35 degrees or less was considered acceptable.
＜発泡性スチレン系樹脂粒子の粉はく離評価＞
発泡性スチレン系樹脂粒子１ｋｇを秤量し、電動篩（ＤＹ－５０）に取り付けた網（目開き：３５５μｍ、４２メッシュ、φ７５０ｍｍ）で、２分間篩い分けを行った。その後、網を通過した粉体を回収し（但し、樹脂が混じっている場合は当該樹脂を除去）、その重量を計量して剥離量とした。そして、下記算出式 （剥離率［重量％］）＝（剥離量［ｇ］）／（発泡性スチレン系樹脂粒子に添加した外添剤の全量［ｇ］）×１００ に基づいて外添剤の剥離率を算出し、剥離率が１０重量％以下である発泡性スチレン系樹脂粒子を合格と評価した
<Powder flaking evaluation of expandable styrene resin particles>
1 kg of expandable styrene resin particles was weighed and sieved for 2 minutes with a mesh (opening: 355 μm, 42 mesh, φ750 mm) attached to an electric sieve (DY-50). After that, the powder that passed through the net was collected (however, if resin was mixed, the resin was removed), and the weight thereof was measured to obtain the peeling amount. Then, the following calculation formula (Peeling rate [% by weight]) = (Peeling amount [g]) / (Total amount of external additive added to expandable styrene resin particles [g]) x 100 The peeling rate was calculated, and the expandable styrene resin particles with a peeling rate of 10% by weight or less were evaluated as acceptable.
＜ブロッキング率の測定＞
攪拌機を備えた加圧式予備発泡機（大開工業（株）製、ＣＨ－１００）に、発泡性ポリスチレン系樹脂粒子を投入し、加熱媒体として水蒸気を用い、吹き込み蒸気圧を０．１ＭＰａとして加熱することによって予備発泡（一次発泡）させ、嵩倍率（見掛け倍率）が６５倍のポリスチレン系予備発泡粒子を得た。そして、予備発泡機からポリスチレン系予備発泡粒子を取り出すときに、当該予備発泡粒子を目開きが１ｃｍの網に通過させ、網を通過しなかった予備発泡粒子を回収し、その重量を計量してブロッキング量とした。そして、下記算出式 ブロッキング率［重量％］＝ブロッキング量［ｇ］／ポリスチレン系予備発泡粒子の全量［ｇ］×１００ に基づいてブロッキング率を算出し、ブロッキング率が２．０重量％以下であるポリスチレン系予備発泡粒子を合格と評価した。
<Measurement of blocking rate>
The expandable polystyrene resin particles are put into a pressurized pre-expanding machine (manufactured by Daikai Kogyo Co., Ltd., CH-100) equipped with a stirrer, and heated using steam as a heating medium at a steam pressure of 0.1 MPa. Pre-expansion (primary expansion) was carried out by this, and polystyrene-based pre-expanded particles having a bulk ratio (apparent ratio) of 65 were obtained. Then, when taking out the pre-expanded polystyrene particles from the pre-expanding machine, the pre-expanded particles are passed through a mesh with an opening of 1 cm, and the pre-expanded particles that have not passed through the mesh are collected and weighed. blocking amount. Then, the blocking rate is calculated based on the following formula: blocking rate [% by weight]=blocking amount [g]/total amount of polystyrene-based pre-expanded particles [g]×100, and the blocking rate is 2.0% by weight or less. The polystyrene-based pre-expanded particles were evaluated as acceptable.
＜予備発泡粒子の帯電量＞
上記で得られた予備発泡粒子を、ポリエチレン袋に１０ｇ投入し、乾燥機４０℃×１時間静置後、約１００回の手振を実施した。手振後、ハ゛ットに払出、静電気測定器スタチロンＤＺ４型(シシド静電気株式会社製)にて、帯電量を測定した。
<Charge amount of pre-expanded particles>
10 g of the pre-expanded particles obtained above were placed in a polyethylene bag, allowed to stand in a dryer at 40° C. for 1 hour, and then shaken about 100 times. After shaking hands, the sample was put out on a tray, and the amount of charge was measured using a static meter Statilon DZ4 (manufactured by Shishido Static Electricity Co., Ltd.).
＜発泡成形体の評価＞
後述する実施例１に記載の製造方法にて得られた発泡成形体を、室温で２４時間乾燥させた後、融着率および表面伸びの評価を行った。
<Evaluation of foam molded product>
A foam molded article obtained by the production method described in Example 1 described later was dried at room temperature for 24 hours, and then evaluated for fusion rate and surface elongation.
（１）融着率の評価
得られた発泡成形体を破断してその破断面を観察し、発泡粒子界面ではなく発泡粒子が破断している割合（融着率）を求めた。融着率が８０％以上である場合を合格と評価した。
(1) Evaluation of Fusion Rate The resulting foamed molded article was broken, and the fractured surface was observed to determine the ratio (fusion rate) at which the foamed particles were broken instead of the foamed particle interfaces. A case where the fusion rate was 80% or more was evaluated as acceptable.
（２）表面のび
得られた発泡成形体の４か所部分の表面の状態を目視で観察して、下記５段階で評価した。その４か所部分の平均値を表面伸びの点数とした。数値の大きい方が発泡粒子同士の隙間が少ない、表面が美麗な状態であり、「４」以上を合格と判定した。
(2) Surface stretch
The state of the surface of the resulting foamed molded product was visually observed at four locations and evaluated according to the following five grades. The average value of the four portions was taken as the surface elongation score. The larger the numerical value, the smaller the gaps between the foamed particles, and the finer the surface.
５：隙間が見当たらない
４：部分的に隙間があるものの、殆ど分からない
３：所々に隙間があるものの、全体としては許容することができる
２：隙間が目立つ
１：隙間が多い。
5: No gaps found 4: Partial gaps but hardly noticeable 3: Some gaps but acceptable overall 2: Conspicuous gaps 1: Many gaps.
以下に、実施例、比較例において使用した塗布剤を記載する。 Coating agents used in Examples and Comparative Examples are described below.
＜液状物Ａ＞
・Ａ（１）；ポリプロピレングリコール：Ｄ－２０００、日本油脂株式会社製
・Ａ（２）；流動パラフィン：Ｋ－３５０、カネダ株式会社製
・Ａ（３）；メチルフェニルポリシロキサン：ＫＦ５０、信越化学工業株式会社製
<Liquid substance A>
A (1); polypropylene glycol: D-2000, manufactured by NOF Co., Ltd. A (2); liquid paraffin: K-350, manufactured by Kaneda Corporation A (3); methylphenyl polysiloxane: KF50, Shin-Etsu Chemical Made by Kogyo Co., Ltd.
＜粘土鉱物Ｂ＞
・Ｂ（１）；タルク：ＰＫ－Ｓ、粒径１１μｍ、林化成株式会社製、
・Ｂ（２）；雲母（マイカ）：ＡＢ－２５Ｓ、粒径１０μｍ、株式会社ヤマグチマイカ製
・Ｂ（３）；カオリン：ＡＳＰ１７０、粒径０．４μｍ、サンエス石膏株式会社製
<Clay mineral B>
· B (1); talc: PK-S, particle size 11 μm, manufactured by Hayashi Kasei Co., Ltd.,
・ B (2); mica (mica): AB-25S, particle size 10 μm, manufactured by Yamaguchi Mica Co., Ltd. ・ B (3); kaolin: ASP170, particle size 0.4 μm, manufactured by Sun-S Gypsum Co., Ltd.
＜融着阻害剤（脂肪酸金属）＞
・Ｂ（４）ステアリン酸亜鉛：粒径１２μｍ、日本油脂株式会社製
<Fusing Inhibitor (Fatty Acid Metal)>
・ B (4) zinc stearate: particle size 12 μm, manufactured by NOF Corporation
＜融着促進剤＞
・Ｃ：ヒドロキシステアリン酸トリグリセリド（ひまし硬化油）：カスターワックス、日本油脂株式会社製
<Fusion Promoter>
・ C: Hydroxystearic acid triglyceride (castor hardened oil): castor wax, manufactured by NOF Co., Ltd.
〔実施例１〕
（発泡性スチレン系樹脂粒子本体）
発泡性スチレン系樹脂粒子（カネパールＴＧ、体積平均粒子径０．９ｍｍ、株式会社カネカ製）の未塗布品を、発泡性スチレン系樹脂粒子本体（基材樹脂）として用いた。当該発泡性ポリスチレン系樹脂粒子本体は、スチレンとアクリル酸ブチルとを重量比９５：５で共重合してなるスチレン－アクリル酸ブチル共重合体である。
[Example 1]
(Body of expandable styrene resin particles)
An uncoated product of expandable styrene resin particles (Kanepal TG, volume average particle size 0.9 mm, manufactured by Kaneka Corporation) was used as an expandable styrene resin particle main body (base resin). The main body of the expandable polystyrene resin particles is a styrene-butyl acrylate copolymer obtained by copolymerizing styrene and butyl acrylate at a weight ratio of 95:5.
（発泡性スチレン系樹脂粒子の製造）
上記の発泡性スチレン系樹脂粒子本体１００重量部をユニバーサルミキサー（（株）ＴＳＭＳ製、ＥＭ－１５Ｂ型）に投入し、液状物Ａ（１）０．０６重量部を６秒間かけて投入し、３０秒間撹拌し、第１塗布工程を終了した。次いで、粘土鉱物Ｂ（１）を０．１５重量部、融着促進剤Ｃを０．０５重量部投入し、さらに３０秒間撹拌し、第２塗布工程を終了し、発泡性スチレン系樹脂粒子を得た。
(Production of expandable styrene resin particles)
100 parts by weight of the above-mentioned expandable styrene resin particle main body was charged into a universal mixer (manufactured by TSMS Co., Ltd., model EM-15B), and 0.06 parts by weight of liquid A (1) was added over 6 seconds, After stirring for 30 seconds, the first coating step was completed. Next, 0.15 parts by weight of the clay mineral B (1) and 0.05 parts by weight of the fusion promoter C are added, and the mixture is stirred for 30 seconds to complete the second coating step, and the expandable styrene resin particles are removed. Obtained.
（予備発泡粒子の製造）
上記で得られた発泡性スチレン系樹脂粒子を、撹拌機を備えた加圧式予備発泡機（大開工業（株）製、ＣＨ－１００）に投入し、加熱媒体として水蒸気（吹き込み蒸気圧６０ｋＰａ）を用い、予備発泡（一次発泡）させ、嵩倍率（見掛け倍率）が６５倍の予備発泡粒子を得た。次いで、得られた予備発泡粒子を室温で２４時間放置して、養生乾燥を行った。
(Production of pre-expanded particles)
The expandable styrene resin particles obtained above are put into a pressurized pre-expanding machine equipped with a stirrer (manufactured by Daikai Kogyo Co., Ltd., CH-100), and water vapor (injection steam pressure 60 kPa) is added as a heating medium. pre-expanded (primary expansion) to obtain pre-expanded particles having a bulk ratio (apparent ratio) of 65 times. Next, the obtained pre-expanded particles were allowed to stand at room temperature for 24 hours for curing drying.
（発泡成形体の製造）
養生乾燥後の予備発泡粒子を、成形機（（株）ダイセン製、ＫＲ－５７）、金型（縦４５０ｍｍ×横３００ｍｍ×深さ２５ｍｍの箱型）を使用して、加熱媒体として水蒸気（吹き込み蒸気圧８０ｋＰａ）を用い、金型内の予備発泡粒子を１０秒間加熱した。次いで、２秒間水冷し、真空放冷し、金型内に設けた面圧計（発泡成形体の圧力）が３０ｋＰａに到達した時点で、金型を開けて発泡成形体を取り出した。
(Manufacturing foam molded product)
The pre-expanded particles after curing and drying are treated with a molding machine (KR-57, manufactured by Daisen Co., Ltd.) and a mold (box type with a length of 450 mm, a width of 300 mm, and a depth of 25 mm). A steam pressure of 80 kPa) was used to heat the pre-expanded particles in the mold for 10 seconds. Then, it was water-cooled for 2 seconds and allowed to stand to cool in a vacuum. When the surface pressure gauge (pressure of the foam-molded product) provided in the mold reached 30 kPa, the mold was opened and the foam-molded product was taken out.
上記で得られた発泡性スチレン系樹脂粒子の樹脂流動性（安息角）及び、粉はく離評価を実施し、かつ、予備発泡粒子の帯電量、発泡成形体の融着率、表面伸びの評価試験を行った。評価結果を表１に示す。 The expandable styrene resin particles obtained above were evaluated for resin fluidity (angle of repose) and powder peeling. did Table 1 shows the evaluation results.
〔実施例２～９，比較例１～３、６～８〕
実施例１で製造した発泡性スチレン系樹脂粒子本体（カネパールＴＧ、株式会社カネカ製）を用い、液状物Ａ、粘土鉱物Ｂ、融着促進剤Ｃ、融着阻害剤（ステアリン酸亜鉛）を表１、２に示す添加量で、実施例１の方法と同様の方法を用いて、発泡性スチレン系樹脂粒子、予備発泡粒子および発泡成形体を得た。評価結果を表１（実施例）、表２（比較例）に示す。
[Examples 2 to 9, Comparative Examples 1 to 3, 6 to 8]
Using the expandable styrene resin particle main body (Kanepal TG, manufactured by Kaneka Corporation) produced in Example 1, liquid A, clay mineral B, fusion accelerator C, and fusion inhibitor (zinc stearate) were prepared. Expandable styrenic resin particles, pre-expanded particles and an expanded molded article were obtained in the same manner as in Example 1 with the addition amounts shown in 1 and 2. The evaluation results are shown in Table 1 (Example) and Table 2 (Comparative Example).
〔実施例１０～１１、比較例４、９〕
発泡性スチレン系樹脂粒子（カネパールＮＳＧ、体積平均粒子径０．９ｍｍ、株式会社カネカ製）の未塗布品を、発泡性スチレン系樹脂粒子本体（基材樹脂）として用いた。当該樹脂粒子本体は、スチレン単独重合体であり、樹脂粒子本体に、非イオン界面活性剤ポリオキシエチレン-モノオレート（Ｏ－３、日本油脂株式会社製）の水溶液を塗布して、乾燥させたもので、樹脂粒子本体の表面にクラックが形成されている。
[Examples 10 to 11, Comparative Examples 4 and 9]
An uncoated product of expandable styrene resin particles (Kanepal NSG, volume average particle size 0.9 mm, manufactured by Kaneka Corporation) was used as an expandable styrene resin particle main body (base resin). The resin particle main body is a styrene homopolymer, which is obtained by applying an aqueous solution of a nonionic surfactant polyoxyethylene monooleate (O-3, manufactured by NOF CORPORATION) to the resin particle main body and drying it. Cracks are formed on the surface of the resin particle body.
この樹脂粒子本体に、粘土鉱物Ｂ、融着促進剤Ｃ、融着阻害剤を、表１、２に示す添加量で、実施例１の方法と同様の方法を用いて、発泡性スチレン系樹脂粒子、予備発泡粒子および発泡成形体を得た。評価結果を表１（実施例）、表２（比較例）に示す。 The clay mineral B, the fusion promoter C, and the fusion inhibitor were added to the resin particle body in the amounts shown in Tables 1 and 2 in the same manner as in Example 1, and an expandable styrene resin was obtained. Particles, pre-expanded particles and foamed moldings were obtained. The evaluation results are shown in Table 1 (Example) and Table 2 (Comparative Example).
〔実施例１２，比較例５，１０〕
発泡性スチレン系樹脂粒子（カネパールＦＱ、体積平均粒子径０．９ｍｍ、株式会社カネカ製）の未塗布品を発泡性スチレン系樹脂粒子本体（基材樹脂）として用いた。当該発泡性ポリスチレン系樹脂粒子は、スチレン、アクリロニトリル、及びαメチルスチレンを重量比７１：２４：５で共重合してなるスチレン－アクリロニトリル－αメチルスチレンの３元共重合体である。当該樹脂粒子本体に、液状物Ａ、粘土鉱物Ｂ、融着促進剤Ｃ、融着阻害剤を、表１に示す添加量で、実施例１の方法と同様の方法を用いて、発泡性熱可塑性樹脂粒子、予備発泡粒子および発泡成形体を得た。評価結果を表１（実施例）、表２（比較例）に示す。
[Example 12, Comparative Examples 5 and 10]
An uncoated product of expandable styrene resin particles (Kanepal FQ, volume average particle size 0.9 mm, manufactured by Kaneka Corporation) was used as an expandable styrene resin particle main body (base resin). The expandable polystyrene resin particles are a styrene-acrylonitrile-α-methylstyrene terpolymer obtained by copolymerizing styrene, acrylonitrile and α-methylstyrene in a weight ratio of 71:24:5. The liquid A, the clay mineral B, the fusion promoter C, and the fusion inhibitor were added to the resin particle body in the amounts shown in Table 1, and foaming heat was applied in the same manner as in Example 1. A plastic resin particle, a pre-expanded particle and an expansion molding were obtained. The evaluation results are shown in Table 1 (Example) and Table 2 (Comparative Example).
表１に示されるとおり、実施例１～１２の発泡性スチレン系樹脂粒子は、良好な流動性（安息角）を示し、かつ、粉はく離の抑制された優れものである。また、予備発泡粒子の製造でのブロッキング率は少なく、予備発泡粒子の帯電性も抑制され、発泡成形体は、良好な融着性および表面伸びを有するものであった。 As shown in Table 1, the expandable styrene resin particles of Examples 1 to 12 exhibited good fluidity (angle of repose) and were excellent in that powder flaking was suppressed. In addition, the blocking rate in the production of the pre-expanded particles was low, the chargeability of the pre-expanded particles was suppressed, and the foamed molded article had good fusion bondability and surface elongation.
これに対し、融着促進剤Ｃが無塗布の比較例１は、発泡成形体の融着率が劣る。液状物Ａを０．４重量部塗布した比較例２は、樹脂の流動性が悪く、ブロッキング率は高くなる。 On the other hand, in Comparative Example 1 in which the fusion promoter C was not applied, the fusion rate of the foam molded product was inferior. In Comparative Example 2, in which 0.4 parts by weight of the liquid A was applied, the fluidity of the resin was poor and the blocking rate was high.
粘土鉱物の代わりにステアリン酸亜鉛を用いた比較例３～５は、粘土鉱物Ｂを用いた実施例８，９,１０に比べて、粉はく離率が高く、予備発泡粒子は大きく負に帯電している。これは、ポリスチレン系樹脂粒子及びステアリン酸亜鉛の負帯電性による、静電反発による粉はく離増加と考えている。又、実施例１のタルクの代わりにステアリン酸亜鉛を用いた比較例６では、予備発泡粒子は負に大きく帯電している。
液状物Ａにシリコーンオイルを用いた比較例７～１０は、予備発泡粒子は負に帯電している。シリコーンオイル自体が大きく負帯電しているためと考えている。
Comparative Examples 3 to 5, in which zinc stearate was used instead of the clay mineral, had a higher powder release rate than Examples 8, 9, and 10, in which clay mineral B was used, and the pre-expanded particles were largely negatively charged. ing. This is believed to be due to an increase in powder flaking due to electrostatic repulsion due to the negative chargeability of the polystyrene resin particles and zinc stearate. In addition, in Comparative Example 6 in which zinc stearate was used instead of talc in Example 1, the pre-expanded particles were highly negatively charged.
In Comparative Examples 7 to 10, in which silicone oil was used as liquid material A, the pre-expanded particles were negatively charged. It is believed that this is because the silicone oil itself is highly negatively charged.
これらの結果から、発泡性スチレン系樹脂粒子本体の表面に、ポリエーテル及び流動パラフィンの少なくともいずれか１種を含む液状物Ａ、粘土鉱物Ｂ、及び、融着促進剤Ｃを塗布してなる発泡性スチレン系樹脂粒子は、流動性を良好な状態に維持し、かつ粉はく離が抑制された発泡性スチレン系樹脂粒子を得ることができ、更に、予備発泡粒子の帯電性を抑制することができる。 From these results, it was found that the surface of the expandable styrene-based resin particles was coated with a liquid A containing at least one of polyether and liquid paraffin, a clay mineral B, and a fusion accelerator C. The flexible styrene resin particles can maintain good fluidity and can provide expandable styrene resin particles in which powder flaking is suppressed, and can also suppress the chargeability of pre-expanded particles. .
Claims (7)
発泡性スチレン系樹脂粒子本体の表面に、前記発泡性スチレン系樹脂粒子本体１００重量部に対して、
ポリエーテル及び流動パラフィンの少なくともいずれか1種を含む液状物（Ａ）が ０．３重量部以下、
粘土鉱物（Ｂ）が０．０１重量部以上１重量部以下、及び、
融着促進剤（Ｃ）が０重量部超０．５重量以下、
が塗布されてなる発泡性スチレン系樹脂粒子。 Expandable styrene resin particles containing a blowing agent,
For 100 parts by weight of the expandable styrene resin particle main body, on the surface of the expandable styrene resin particle main body,
0.3 parts by weight or less of the liquid (A) containing at least one of polyether and liquid paraffin,
0.01 parts by weight or more and 1 part by weight or less of the clay mineral (B), and
The fusion promoter (C) is more than 0 parts by weight and 0.5 parts by weight or less,
Expandable styrene resin particles coated with
前記ポリエーテルは、ポリプロピレングリコール及びポリエチレングリコールの少なくともいずれか１種を含有する、請求項1に記載の発泡性スチレン系樹脂粒子。 The liquid material (A) contains a polyether that is sparingly soluble in water,
2. The expandable styrenic resin particles according to claim 1, wherein the polyether contains at least one of polypropylene glycol and polyethylene glycol.
前記発泡性スチレン系樹脂粒子本体の表面に、前記発泡性スチレン系樹脂粒子本体 １００重量部に対して、
ポリエーテル及び流動パラフィンの少なくともいずれか1種を含む液状物（Ａ）を、０．３重量部以下、
粘土鉱物（Ｂ）を、０．０１重量部以上１重量部以下、及び、
融着促進剤（Ｃ）を、０重量部超０．５重量以下、
塗布する塗布工程と、を含む発泡性スチレン系樹脂粒子の製造方法。
a step of obtaining an expandable styrene-based resin particle body containing a blowing agent;
For 100 parts by weight of the expandable styrene resin particle main body, on the surface of the expandable styrene resin particle main body,
0.3 parts by weight or less of a liquid (A) containing at least one of polyether and liquid paraffin,
0.01 parts by weight or more and 1 part by weight or less of the clay mineral (B), and
a fusion promoter (C) of more than 0 parts by weight and 0.5 parts by weight or less;
and a coating step of coating.
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