JP2007246705A - Foamable styrenic resin particle and method for producing styrenic resin foamed molded article - Google Patents
Foamable styrenic resin particle and method for producing styrenic resin foamed molded article Download PDFInfo
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Abstract
Description
本発明は、発泡剤を含有するスチレン系樹脂からなる発泡成形品製造用の発泡性スチレン系樹脂粒子に関し、特に、成形サイクルが短く、且つ十分な強度を持ち、光沢のある表面を持った発泡成形品が得られる発泡性スチレン系樹脂粒子、これを用いるスチレン系樹脂発泡成形品の製造方法に関する。 The present invention relates to an expandable styrene resin particle for producing a foam molded article comprising a styrene resin containing a foaming agent, and in particular, a foam having a short molding cycle, sufficient strength, and a glossy surface. The present invention relates to an expandable styrene resin particle from which a molded product can be obtained, and a method for producing a styrene resin foam molded product using the same.
従来、発泡成形品製造時の成形サイクルの短縮化を企図した発泡性スチレン系樹脂粒子の提案としては、例えば、特許文献１〜５に記載された技術が知られている。
特許文献１には、脂肪族カルボン酸と脂肪族アルコールのエステル（このエステルは、分子中に水酸基を有せず、常温で固体状である。）または該エステルと微粉滑剤の混合物を発泡性スチレン系樹脂粒子表面に被覆してなる新規発泡性スチレン系樹脂粒子が開示されている。
Conventionally, for example, the techniques described in Patent Documents 1 to 5 are known as proposals of expandable styrene-based resin particles intended to shorten the molding cycle at the time of manufacturing a foam molded product.
Patent Document 1 discloses an ester of an aliphatic carboxylic acid and an aliphatic alcohol (this ester does not have a hydroxyl group in the molecule and is solid at normal temperature) or a mixture of the ester and a fine powder lubricant. A novel expandable styrene resin particle formed by coating the surface of a resin particle is disclosed.
特許文献２には、発泡性ポリスチレン粒子１００質量部の表面を、０．００５〜０．０５質量部の液状ポリシロキサン及び０．０１〜０．２０質量部のＲ１−ＣＯ−ＮＨＲ２（Ｒ１＝Ｃ６〜Ｃ２２のアルキル基、Ｒ２＝Ｈ又はＣ１〜Ｃ４アルキル基又はヒドロオキシアルキル基）で被覆したことを特徴とする発泡性ポリスチレン粒子が開示されている。 Patent Document 2 discloses that the surface of 100 parts by mass of expandable polystyrene particles is 0.005 to 0.05 parts by mass of liquid polysiloxane and 0.01 to 0.20 parts by mass of R 1 —CO—NHR 2 (R 1 = alkyl group of C 6 -C 22, expandable polystyrene particles are disclosed, wherein the coated with R 2 = H or C 1 -C 4 alkyl or hydro-oxy group).
特許文献３には、揮発性膨張剤を含有する発泡性スチレン系樹脂粒子の表面に、融点が４５〜１８０℃であり、予備発泡時の樹脂粒子同士のブロッキング防止と発泡成形時の冷却時間を短縮させる効果のある表面改質剤を被覆する方法において、該表面改質剤を発泡性スチレン系樹脂粒子表面に付着させるバインダーとしてシリコンオイルを用いることを特徴とする表面改質発泡性スチレン系樹脂粒子の製造方法が開示されている。また、特許文献３の表１中の実施例には、ステアリン酸亜鉛と表面改質剤とメチルフェニルポリシロキサンとを含むコーティング剤を表面に付着させてなる発泡性スチレン系樹脂粒子が開示されている。 In Patent Document 3, the surface of expandable styrene resin particles containing a volatile expansion agent has a melting point of 45 to 180 ° C., and prevents blocking between resin particles during preliminary foaming and cooling time during foam molding. A surface-modified foaming styrenic resin characterized by using silicon oil as a binder for adhering the surface modifying agent to the surface of foamable styrenic resin particles in a method of coating a surface modifying agent having an effect of shortening A method for producing particles is disclosed. Further, Examples in Table 1 of Patent Document 3 disclose expandable styrene resin particles in which a coating agent containing zinc stearate, a surface modifier, and methylphenylpolysiloxane is adhered to the surface. Yes.
特許文献４には、発泡剤を含有する発泡性ポリスチレン系樹脂粒子であって、ポリジメチルシロキサンを粒子の表面層付近において最も多量となるように含有してなるとともに、表面がフェニル基を含むシリコンオイルによって被覆されていることを特徴とする発泡性ポリスチレン系樹脂粒子が開示されている。また、特許文献４の第１表中の実施例には、発泡剤と共にポリジメチルシロキサンを発泡性ポリスチレン系樹脂粒子に含浸させた後、フェニル基を含むシリコンオイルを粒子表面に塗布したものが例示されている。 Patent Document 4 discloses expandable polystyrene-based resin particles containing a foaming agent, containing polydimethylsiloxane in the largest amount in the vicinity of the surface layer of the particles, and having a surface containing a phenyl group. An expandable polystyrene resin particle characterized by being covered with oil is disclosed. Further, the examples in Table 1 of Patent Document 4 are examples in which polydimethylsiloxane is impregnated with expandable polystyrene resin particles together with a foaming agent, and then silicon oil containing phenyl groups is applied to the particle surfaces. Has been.
特許文献５には、熱可塑性樹脂（Ａ）、フェニル基をシリコン上の置換基として有するポリシロキサン（Ｂ）、臭素系難燃剤（Ｃ）および発泡剤（Ｄ）を必須な成分として含有することを特徴とする発泡性難燃性樹脂組成物が開示されている。
しかしながら、前述した従来技術には、次のような問題があった。
特許文献１記載の従来技術では、発泡時に発泡粒子の表面気泡に亀裂を入れて成形時の発泡剤拡散を促進するため、成形サイクルは短くなるが、表面気泡の亀裂のために成形品の強度が低下し、割れやすくなる問題がある。
また、前記亀裂のために成形品表面の光沢が無くなり、外観が悪化する問題がある。
また、混合物を多量に被覆すると、成形時の発泡力低下により発泡粒子同士の融着性が悪化する問題がある。
However, the above-described conventional technique has the following problems.
In the prior art described in Patent Document 1, since the surface bubbles of the foamed particles are cracked at the time of foaming to promote the diffusion of the foaming agent at the time of molding, the molding cycle is shortened. There is a problem that it is lowered and easily broken.
In addition, the surface of the molded article loses its gloss due to the cracks, and the appearance is deteriorated.
Further, when a large amount of the mixture is coated, there is a problem that the fusion property between the expanded particles is deteriorated due to a decrease in the foaming force at the time of molding.
特許文献２記載の従来技術では、ポリシロキサンによるブロッキング防止と脂肪酸アミドによる融着性向上の組み合わせであり、特定のメチルフェニルシリコーンオイルによる成形サイクル短縮、及び低圧での融着性向上については、なんら示唆されていない。また、実施例の表２中のＲｕｎ６では、メチルフェニルポリシロキサンもジメチルポリシロキサンと同様に融着を阻害している。なお、その場合の成形蒸気圧力、成形サイクルについては記載が無く、使用発泡剤についても実施例でペンタンを用いていることが記載されているのみである。 In the prior art described in Patent Document 2, it is a combination of blocking prevention by polysiloxane and improvement of fusion property by fatty acid amide. About shortening of molding cycle by specific methylphenyl silicone oil and improvement of fusion property at low pressure Not suggested. Further, in Run 6 in Table 2 of the examples, methylphenylpolysiloxane also inhibits fusion in the same manner as dimethylpolysiloxane. In this case, there is no description about the molding steam pressure and the molding cycle, and it is only described that pentane is used in the examples for the foaming agent used.
特許文献３記載の従来技術では、ブロッキング防止と成形時冷却時間短縮効果のある表面改質剤を発泡性スチレン系樹脂粒子表面に被覆する際、シリコンオイルを表面改質剤のバインダーとして用いている。この従来技術では、表面改質剤の剥離が少なく成形サイクルを短縮できるが、表面改質剤により成形品の表面気泡に微細な亀裂が入るため、成形品の光沢が無くなり、強度も低下し、割れやすくなる問題がある。
また、特許文献３の第３頁には、バインダーのシリコンオイルとして、２５℃の粘度が３０００センチストークス以下、好ましくは１０〜１０００センチストークスのシリコンオイル、中でも水酸基を有しないメチルフェニルポリシロキサンが特に好ましいとの記載があるが、０．１質量％を超える添加は成形時の発泡粒子同士の融着性が阻害されると記載されており、特定のメチルフェニルシリコーンオイルによる成形サイクル短縮、及び低圧での融着性向上については、なんら示唆されていない。また、実施例における成形条件は、０．７ｋｇｆ／ｃｍ２Ｇの水蒸気で１０秒加熱することが記載されている。
In the prior art described in Patent Document 3, silicon oil is used as a binder for the surface modifier when coating the surface modifier having the effect of preventing blocking and shortening the cooling time during molding on the surface of the expandable styrene resin particles. . In this prior art, the surface modifier is less peeled and the molding cycle can be shortened, but the surface modifier causes fine cracks in the surface bubbles of the molded product, so the gloss of the molded product is lost and the strength is also reduced. There is a problem that breaks easily.
Further, on page 3 of Patent Document 3, as the silicone oil of the binder, a silicone oil having a viscosity at 25 ° C. of 3000 centistokes or less, preferably 10 to 1000 centistokes, particularly methylphenylpolysiloxane having no hydroxyl group is particularly preferred. Although there is a description that it is preferable, it is described that the addition of more than 0.1% by mass inhibits the fusibility between expanded particles at the time of molding, shortening the molding cycle with a specific methylphenyl silicone oil, and low pressure There is no suggestion about improvement of the fusion property in the case. In addition, the molding conditions in the examples describe heating for 10 seconds with 0.7 kgf / cm 2 G of water vapor.
特許文献４記載の従来技術では、ポリジメチルシロキサンを発泡性スチレン系樹脂粒子の表層付近に最も多量となるように含有させ、かつフェニル基を含むシリコンオイルを表面に被覆することで、公知のサイクル短縮剤のように発泡成形品の表面気泡に微細な亀裂を発生させないため、成形品強度及び光沢が低下する恐れがない。しかし、ポリジメチルシロキサンを粒子表層付近に最も多量となるように含浸させなければならないため、実験室ではともかく、工業生産では、ポリジメチルシロキサンの含浸条件の調整が難しく、再現性が十分に得られない問題がある。
また、含浸条件の調整が難しいことに加えて、ポリジメチルシロキサンの含浸に長時間を要するため、生産性が悪い。実施例ではポリジメチルシロキサン（ＫＦ−９６、粘度１００ｃｓ）の含浸に１００℃×１２時間を要している。
また、ポリジメチルシロキサンを含浸させずにメチルフェニルシリコンオイルを表面に被覆した例示（比較例２）では、成形サイクルは短縮されておらず、特定のメチルフェニルシリコンオイルによる成形サイクル短縮、及び低圧での融着性向上については、なんら示唆されていない。
In the prior art described in Patent Document 4, polydimethylsiloxane is contained in the vicinity of the surface layer of the expandable styrenic resin particles so as to be the most abundant, and a silicon oil containing a phenyl group is coated on the surface, so that a known cycle can be obtained. Unlike the shortening agent, fine cracks are not generated in the surface bubbles of the foam-molded product, so that the strength and gloss of the molded product are not reduced. However, since polydimethylsiloxane must be impregnated in the vicinity of the particle surface layer so that it is the largest amount, in industrial production, it is difficult to adjust the impregnation conditions of polydimethylsiloxane and sufficient reproducibility is obtained. There is no problem.
In addition, it is difficult to adjust the impregnation conditions, and it takes a long time to impregnate polydimethylsiloxane, so that productivity is poor. In the examples, impregnation with polydimethylsiloxane (KF-96, viscosity 100 cs) requires 100 ° C. × 12 hours.
Further, in the example (Comparative Example 2) in which methylphenyl silicone oil is coated on the surface without impregnating with polydimethylsiloxane, the molding cycle is not shortened, the molding cycle is shortened with a specific methylphenyl silicone oil, and the pressure is low. There is no suggestion of improving the fusing property.
特許文献５記載の従来技術は、発明の目的が難燃性の向上であり、特定のメチルフェニルシリコーンオイルによる成形サイクル短縮、及び低圧での融着性向上については、なんら示唆されていない。
また臭素系難燃剤、及びトルエンを含有した発泡性スチレン系樹脂粒子に、この特定のメチルフェニルシリコーンオイルを被覆すると、成形サイクル短縮効果が小さく、成形品の融着性が悪化する傾向があり好ましくない。
In the prior art described in Patent Document 5, the object of the invention is to improve the flame retardancy, and there is no suggestion about shortening the molding cycle with a specific methylphenyl silicone oil and improving the fusion property at low pressure.
Further, when this specific methylphenyl silicone oil is coated on the expandable styrene resin particles containing bromine-based flame retardant and toluene, the effect of shortening the molding cycle is small, and the fusion property of the molded product tends to deteriorate. Absent.
本発明は、前記事情に鑑みてなされ、成形サイクルが短く、且つ十分な強度を持ち、光沢のある表面を持った発泡成形品が得られる発泡性スチレン系樹脂粒子の提供を目的とする。 This invention is made | formed in view of the said situation, and it aims at provision of the expandable styrene-type resin particle from which the molding cycle is short, has sufficient intensity | strength, and can obtain the foaming molded article with the glossy surface.
本発明は、前記目的を達成するため、発泡剤を含有するスチレン系樹脂からなり、嵩発泡倍数６０倍に発泡させたときの発泡粒子表層部の平均気泡径Ｄが、４０μｍ≦Ｄ≦１５０μｍの関係を満たす発泡性スチレン系樹脂粒子本体１００質量部に対して、２５℃での屈折率が１．４５以上であるメチルフェニルシリコーンオイル０．０１〜０．２質量部と、高級脂肪酸の金属塩０．０５〜０．２質量部とが粒子表面に被覆され、かつ、分子中に水酸基を有しない高級脂肪酸トリグリセライドの被覆量が０．０５質量部未満であることを特徴とする発泡性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 made of a styrene resin containing a foaming agent, and the average cell diameter D of the surface layer of the expanded particles when expanded to a bulk expansion ratio of 60 times is 40 μm ≦ D ≦ 150 μm. 0.01 to 0.2 parts by mass of methylphenyl silicone oil having a refractive index at 25 ° C. of 1.45 or more with respect to 100 parts by mass of the expandable styrene resin particle main body satisfying the relationship, and a metal salt of a higher fatty acid Expandable styrene-based, characterized in that 0.05 to 0.2 parts by mass is coated on the particle surface, and the coating amount of higher fatty acid triglyceride having no hydroxyl group in the molecule is less than 0.05 parts by mass Resin particles are provided.
本発明の発泡性スチレン系樹脂粒子において、前記発泡性スチレン系樹脂粒子を加熱して得られた予備発泡粒子を成形型のキャビティ内に充填し、蒸気圧０．０５ＭＰａＧで型内発泡成形して得られた発泡倍数６０倍の発泡成形品の曲げ強度（ＪＩＳ Ａ９５１１）が０．２５ＭＰａ以上であることが好ましい。より好ましくは０．２９ＭＰａ以上である。 In the expandable styrenic resin particles of the present invention, pre-expanded particles obtained by heating the expandable styrene resin particles are filled in a cavity of a mold, and subjected to in-mold foam molding at a vapor pressure of 0.05 MPaG. It is preferable that the bending strength (JIS A9511) of the obtained foamed molded product having a foam expansion ratio of 60 times is 0.25 MPa or more. More preferably, it is 0.29 MPa or more.
本発明の発泡性スチレン系樹脂粒子において、前記発泡性スチレン系樹脂粒子を加熱して得られた予備発泡粒子を成形型のキャビティ内に充填し、蒸気圧０．０５ＭＰａＧで型内発泡成形して得られた発泡倍数６０倍の発泡成形品の表面光沢度（ＪＩＳ Ｚ８７４１、６０°／６０°）が２５以上であることが好ましい。より好ましくは３０以上である。 In the expandable styrenic resin particles of the present invention, pre-expanded particles obtained by heating the expandable styrene resin particles are filled in a cavity of a mold, and subjected to in-mold foam molding at a vapor pressure of 0.05 MPaG. It is preferable that the surface glossiness (JIS Z8741, 60 ° / 60 °) of the obtained foamed molded product having an expansion ratio of 60 times is 25 or more. More preferably, it is 30 or more.
本発明の発泡性スチレン系樹脂粒子において、嵩発泡倍数Ｘ倍に発泡させたときの発泡粒子表層部の平均気泡径Ｄ’を、次式（１） In the expandable styrenic resin particles of the present invention, the average cell diameter D ′ of the surface layer of the expanded particles when expanded to a bulk expansion ratio X times is expressed by the following formula (1):
（式中、Ｄは嵩発泡倍数６０倍に換算した発泡粒子表層部の平均気泡径（μｍ）を表し、Ｄ’は嵩発泡倍数Ｘ倍に発泡させたときの発泡粒子表層部の平均気泡径（μｍ）を表す）を用いて嵩発泡倍数６０倍に換算した発泡粒子表層部の平均気泡径Ｄが、４０μｍ≦Ｄ≦１５０μｍの関係を満たすことが好ましい。 (In the formula, D represents the average cell diameter (μm) of the foamed particle surface layer part converted to a bulk foaming magnification of 60 times, and D ′ is the average cell diameter of the foamed particle surface layer part when foamed to the bulk foaming factor X times) It is preferable that the average cell diameter D of the surface portion of the expanded particle converted to a bulk expansion ratio of 60 times using (represents (μm)) satisfies the relationship of 40 μm ≦ D ≦ 150 μm.
本発明の発泡性スチレン系樹脂粒子において、トルエン及び臭素系難燃剤を含有せず、発泡助剤としてシクロヘキサンをスチレン系樹脂１００質量部に対し０．５〜１．５質量部の範囲で含むことが好ましい。 The expandable styrene resin particles of the present invention do not contain toluene and bromine flame retardant, and contain cyclohexane as a foaming aid in the range of 0.5 to 1.5 parts by mass with respect to 100 parts by mass of the styrene resin. Is preferred.
また本発明は、前述した本発明に係る発泡性スチレン系樹脂粒子を加熱して得られた予備発泡粒子を成形型のキャビティ内に充填し、型内発泡成形してスチレン系樹脂発泡成形品を得ることを特徴とするスチレン系樹脂発泡成形品の製造方法を提供する。 The present invention also provides a pre-expanded particle obtained by heating the expandable styrenic resin particles according to the present invention described above, filled in a cavity of a molding die, and subjected to in-mold foam molding to obtain a styrene resin foam molded product. A method for producing a styrenic resin foam-molded article is provided.
本発明のスチレン系樹脂発泡成形品の製造方法において、発泡倍数が２０〜９０倍の範囲内であることが好ましい。 In the method for producing a styrene resin foam molded article of the present invention, the expansion ratio is preferably in the range of 20 to 90 times.
本発明の発泡性スチレン系樹脂粒子は、発泡剤を含有するスチレン系樹脂からなり、嵩発泡倍数６０倍に発泡させたときの発泡粒子表層部の平均気泡径Ｄが、４０μｍ≦Ｄ≦１５０μｍの関係を満たす発泡性スチレン系樹脂粒子本体１００質量部に対して、２５℃での屈折率が１．４５以上であるメチルフェニルシリコーンオイル０．０１〜０．２質量部と、高級脂肪酸の金属塩０．０５〜０．２質量部とが粒子表面に被覆され、かつ、分子中に水酸基を有しない高級脂肪酸トリグリセライドの被覆量が０．０５質量部未満としたものなので、この発泡性スチレン系樹脂粒子を加熱して得られた予備発泡粒子を成形型のキャビティ内に充填し、型内発泡成形してスチレン系樹脂発泡成形品を得る際に、従来の型内発泡成形で使用するより低圧の蒸気でも発泡粒子同士を十分融着させることができ、低圧の蒸気で成形を行うことにより、成形時の冷却時間が短くなり、短い成形サイクルでも、十分な強度を持ち、表面光沢に優れた発泡成形品を得ることができる。 The expandable styrene resin particles of the present invention are made of a styrene resin containing a foaming agent, and the average cell diameter D of the expanded particle surface layer when expanded to a bulk expansion ratio of 60 times is 40 μm ≦ D ≦ 150 μm. 0.01 to 0.2 parts by mass of methylphenyl silicone oil having a refractive index at 25 ° C. of 1.45 or more with respect to 100 parts by mass of the expandable styrene resin particle main body satisfying the relationship, and a metal salt of a higher fatty acid Since the coating amount of the higher fatty acid triglyceride having 0.05 to 0.2 parts by mass on the particle surface and having no hydroxyl group in the molecule is less than 0.05 parts by mass, this expandable styrenic resin When the pre-expanded particles obtained by heating the particles are filled into the mold cavity and foam-molded in the mold to obtain a styrene resin foam-molded product, the pressure is lower than that used in conventional in-mold foam molding. Foamed particles can be sufficiently fused together with steam, and by molding with low-pressure steam, the cooling time during molding is shortened. Foam with sufficient strength and excellent surface gloss even in a short molding cycle A molded product can be obtained.
本発明の発泡性スチレン系樹脂粒子は、嵩発泡倍数６０倍に発泡させたときの発泡粒子表層部の平均気泡径Ｄが、４０μｍ≦Ｄ≦１５０μｍの関係を満たす発泡性スチレン系樹脂粒子本体１００質量部に対して、２５℃での屈折率が１．４５以上であるメチルフェニルシリコーンオイル０．０１〜０．２質量部と、高級脂肪酸の金属塩０．０５〜０．２質量部とを含む被覆剤が粒子表面に被覆され、かつ、分子中に水酸基を有しない高級脂肪酸トリグリセライドの被覆量が０．０５質量部未満であることを特徴としている。 The expandable styrenic resin particles of the present invention have a foamed styrene resin particle main body 100 in which the average cell diameter D of the foamed particle surface layer portion when expanded to a bulk expansion ratio of 60 times satisfies the relationship of 40 μm ≦ D ≦ 150 μm. 0.01 to 0.2 parts by mass of methylphenyl silicone oil having a refractive index of 1.45 or more at 25 ° C. and 0.05 to 0.2 parts by mass of a metal salt of a higher fatty acid with respect to parts by mass It is characterized in that the coating amount of the higher fatty acid triglyceride which is coated on the particle surface and has no hydroxyl group in the molecule is less than 0.05 parts by mass.
本発明の発泡性スチレン系樹脂粒子を構成する樹脂素材としては、例えばスチレンのほか、α−メチルスチレン、ビニルトルエン、パラクロロスチレン等のスチレン誘導体が挙げられる。その他には、例えば、アクリロニトリル、アクリル酸、アクリル酸エステル、メタクリル酸エステル等のスチレンと共重合可能な単量体やジビニルベンゼン等の架橋性単量体を併用することもできるが、スチレン成分が５０質量％以上である共重体またはスチレン単独重合体であるのが好ましい。 Examples of the resin material constituting the expandable styrene resin particles of the present invention include styrene derivatives such as α-methylstyrene, vinyltoluene, and parachlorostyrene in addition to styrene. In addition, for example, a monomer copolymerizable with styrene such as acrylonitrile, acrylic acid, acrylic acid ester, methacrylic acid ester, or a crosslinkable monomer such as divinylbenzene can be used in combination. A copolymer or styrene homopolymer of 50% by mass or more is preferable.
また、スチレン系樹脂粒子を得るためには、一般的な懸濁重合法や押出ペレット法等の公知の方法が使用できる。これらのスチレン系樹脂粒子にプロパン、ブタン、ペンタン等の発泡剤を適宜含有させて発泡性スチレン系樹脂粒子とすることができる。また、発泡剤を含有させる方法としては、重合の途中乃至重合終了後に発泡剤を添加して含有させる方法、また、押出途中で発泡剤を添加して含有させる方法等であってもよい。さらに、必要に応じてシクロヘキサンや可塑剤等の発泡助剤、その他公知の添加剤を添加することもできる。さらに、本発明に使用するスチレン系樹脂には、必要に応じて、染料等の着色剤、酸化防止剤、難燃剤、帯電防止剤等の各種添加剤を添加することができる。 Moreover, in order to obtain a styrene-type resin particle, well-known methods, such as a general suspension polymerization method and an extrusion pellet method, can be used. These styrene resin particles can be made into expandable styrene resin particles by appropriately containing a foaming agent such as propane, butane and pentane. Moreover, as a method of containing a foaming agent, the method of adding and containing a foaming agent in the middle of superposition | polymerization thru | or completion | finish of polymerization, the method of adding and making a foaming agent in the middle of extrusion, etc. may be sufficient. Further, if necessary, foaming aids such as cyclohexane and plasticizer, and other known additives can be added. Furthermore, various additives such as a colorant such as a dye, an antioxidant, a flame retardant, and an antistatic agent can be added to the styrenic resin used in the present invention, if necessary.
前記発泡性スチレン系樹脂粒子本体は、嵩発泡倍数６０倍に発泡させたときの発泡粒子表層部の平均気泡径Ｄが、４０μｍ≦Ｄ≦１５０μｍの関係を満たしている。前記Ｄが４０μｍ未満であると、得られる発泡性スチレン系樹脂粒子を加熱して得られた予備発泡粒子を成形型のキャビティ内に充填し、型内発泡成形（以下、予備発泡−型内発泡成形と記す。）し、スチレン系樹脂発泡成形品を得る際に、発泡粒子同士の融着率が低下し、得られるスチレン系樹脂発泡成形品の曲げ強度が低くなる。一方、前記Ｄが１５０μｍを超えると、得られる発泡性スチレン系樹脂粒子を予備発泡−型内発泡成形し、スチレン系樹脂発泡成形品を得る際に、成形サイクル短縮効果が小さく、また気泡径が大きすぎるために曲げ強度の劣る発泡成形品となる。より好ましくは５０μｍ≦Ｄ≦１３０μｍの関係を満たすものである。 The foamable styrenic resin particle main body satisfies the relationship of 40 μm ≦ D ≦ 150 μm in the average cell diameter D of the surface layer portion of the expanded particle when expanded to a bulk expansion ratio of 60 times. When D is less than 40 μm, pre-expanded particles obtained by heating the resulting expandable styrene resin particles are filled in a cavity of a mold, and in-mold foam molding (hereinafter referred to as pre-foam-in-mold foam). When the styrene resin foam molded product is obtained, the fusion rate between the foamed particles is lowered, and the bending strength of the resulting styrene resin foam molded product is lowered. On the other hand, when D exceeds 150 μm, when the foamable styrene resin particles obtained are prefoamed and subjected to in-mold foam molding to obtain a styrene resin foam molded article, the molding cycle shortening effect is small, and the cell diameter is small. Since it is too large, it becomes a foam-molded product having inferior bending strength. More preferably, the relationship of 50 μm ≦ D ≦ 130 μm is satisfied.
本発明の発泡性スチレン系樹脂粒子において、発泡粒子の嵩発泡倍数が６０倍に満たない、或いは６０倍を超える場合は、前述した式（１）を用い、嵩発泡倍数Ｘ倍に発泡させたときの発泡粒子表層部の平均気泡径Ｄ’（μｍ）を嵩発泡倍数６０倍に発泡させたときの発泡粒子表層部の平均気泡径Ｄ（μｍ）に換算して求めることができる。発泡による体積変化は３次元の変化なので、３乗根することにより１次元の気泡径を求めることができる。 In the expandable styrenic resin particles of the present invention, when the expanded foam volume of the expanded particles is less than 60 times or exceeds 60 times, the above-described formula (1) is used to expand the expanded foam volume to X times. The average cell diameter D ′ (μm) of the foamed particle surface layer part can be converted into the average cell diameter D (μm) of the foamed particle surface layer part when foamed to a bulk expansion ratio of 60 times. Since the volume change due to foaming is a three-dimensional change, the one-dimensional bubble diameter can be obtained by taking the cube root.
本発明の発泡性スチレン系樹脂粒子の被覆剤に用いるメチルフェニルシリコーンオイルは、ＪＩＳ Ｋ００６２に基づいて、アッベ屈折計を用いて測定した、２５℃での屈折率が１．４５以上、好ましくは１．４９以上のものである。本発明では、屈折率が１．４５以上のメチルフェニルシリコーンオイルを発泡性スチレン系樹脂粒子本体１００質量部に対して０．０１〜０．２質量部を粒子表面に被覆する。これによって、発泡性スチレン系樹脂粒子を予備発泡−型内発泡成形する際、成形蒸気圧が通常の型内発泡成形条件（例えば、０．０７ＭＰａＧ）よりも低くした低圧成形時（例えば、０．０６ＭＰａＧ〜０．０５ＭＰａＧ）であっても、発泡粒子同士が十分に融着し、曲げ強度などの機械的性質が良好な発泡成形品を製造することができる。その結果、成形蒸気圧を通常の成形条件よりも下げて発泡成形を行うことで、成形後の冷却時間を短縮でき、成形サイクルを短縮することができる。メチルフェニルシリコーンオイルの量が０．０１質量部未満であると、低圧成形時の発泡粒子同士の融着率が不十分となり、成形サイクルの短縮化が不可能になる。またメチルフェニルシリコーンオイルの量が０．２質量部を超えると、前述した効果が頭打ちとなり、コストが上昇すること、およびベタツキが大きくなり、被覆した発泡性樹脂粒子の流動性が悪くなることから、好ましくない。 The methylphenyl silicone oil used for the coating agent for the expandable styrene resin particles of the present invention has a refractive index of 1.45 or more, preferably 1 measured at 25 ° C. using an Abbe refractometer based on JIS K0062. .49 or more. In the present invention, 0.01 to 0.2 parts by mass of methylphenyl silicone oil having a refractive index of 1.45 or more is coated on the particle surface with respect to 100 parts by mass of the foamable styrene resin particle body. As a result, when the expandable styrenic resin particles are subjected to pre-expansion-in-mold foam molding, the molding vapor pressure is lower than the normal in-mold foam molding conditions (for example, 0.07 MPaG) (for example, 0.00. Even if it is 06 MPaG to 0.05 MPaG), the foamed particles can be sufficiently fused together to produce a foamed molded article having good mechanical properties such as bending strength. As a result, by performing the foam molding with the molding vapor pressure lower than the normal molding conditions, the cooling time after molding can be shortened and the molding cycle can be shortened. When the amount of methylphenyl silicone oil is less than 0.01 parts by mass, the fusion rate between the expanded particles at the time of low-pressure molding becomes insufficient, and the molding cycle cannot be shortened. Further, if the amount of methylphenyl silicone oil exceeds 0.2 parts by mass, the above-mentioned effects reach a peak, resulting in an increase in cost and stickiness, and the fluidity of the coated foamed resin particles becomes poor. It is not preferable.
このようなメチルフェニルシリコーンオイルは、ジメチルポリシロキサンのメチル基の一部をフェニル基に置換したもので、一般にフェニル基の含有量が増加する程、屈折率は大きくなる関係にあるため、ある一定量以上のフェニル基を含有するメチルフェニルシリコーンオイルが、低圧成形時の融着促進に効果を有するものと考えられる。また、メチルフェニルシリコーンオイルは、無色透明で、２５℃での粘度が５００ｍｍ２／ｓ以下が好ましく、これを越えると発泡性スチレン系樹脂粒子表面に均一に被覆することが困難になる。また、屈折率が１．４５未満のメチルフェニルシリコーンオイル、及びジメチルシリコーンオイル（市販品の屈折率は１．３８〜１．４０程度である）では、低圧成形時の融着促進効果が得られず、成形サイクルも短縮できない。 Such a methylphenyl silicone oil is obtained by substituting a part of the methyl group of dimethylpolysiloxane with a phenyl group. Generally, as the phenyl group content increases, the refractive index increases, so there is a certain constant. It is considered that methyl phenyl silicone oil containing an amount of phenyl groups or more has an effect on promoting fusion during low-pressure molding. The methylphenyl silicone oil is colorless and transparent, and preferably has a viscosity at 25 ° C. of 500 mm 2 / s or less. If the methylphenyl silicone oil exceeds this, it becomes difficult to uniformly coat the surface of the expandable styrene resin particles. Also, methyl phenyl silicone oil having a refractive index of less than 1.45 and dimethyl silicone oil (the refractive index of commercially available products is about 1.38 to 1.40) can provide an effect of promoting fusion during low-pressure molding. In addition, the molding cycle cannot be shortened.
本発明の発泡性スチレン系樹脂粒子の被覆剤に用いる高級脂肪酸の金属塩としては、例えば、ステアリン酸マグネシウム、ステアリン酸カルシウム、ステアリン酸亜鉛、ステアリン酸バリウム、ステアリン酸アルミニウム、ステアリン酸リチウム、ラウリン酸亜鉛、ラウリン酸バリウムなどが挙げられ、これらの中でもステアリン酸亜鉛が好ましい。この高級脂肪酸の金属塩は、発泡性スチレン系樹脂粒子本体１００質量部に対して、０．０５〜０．２質量部の範囲内で粒子表面に被覆する。この高級脂肪酸の金属塩を前記範囲内の量で被覆することによって、発泡成形時に発泡粒子同士の融着を損なうことなく、予備発泡粒子の流動性を向上させることができる。一方、高級脂肪酸の金属塩の量が前記範囲未満であると、予備発泡粒子の流動性が悪くなり、また発泡時に結合する粒子が出やすく、成形型内への充填不良が発生する恐れがある。また高級脂肪酸の金属塩の量が前記範囲を超えると、発泡成形品の発泡粒子同士の融着率が悪くなり、曲げ強度が不十分となる恐れがあり、これは特に低圧成形時に顕著となる。 Examples of the metal salt of higher fatty acid used in the coating agent for expandable styrene resin particles of the present invention include magnesium stearate, calcium stearate, zinc stearate, barium stearate, aluminum stearate, lithium stearate, zinc laurate. And barium laurate. Among these, zinc stearate is preferable. The metal salt of the higher fatty acid covers the particle surface within a range of 0.05 to 0.2 parts by mass with respect to 100 parts by mass of the expandable styrene resin particle main body. By coating the metal salt of this higher fatty acid in an amount within the above range, the fluidity of the pre-expanded particles can be improved without impairing the fusion between the expanded particles during foam molding. On the other hand, if the amount of the metal salt of the higher fatty acid is less than the above range, the fluidity of the pre-expanded particles is deteriorated, and particles that are bonded at the time of foaming are likely to be produced, which may cause poor filling in the mold. . If the amount of the higher fatty acid metal salt exceeds the above range, the fusion rate between the foamed particles of the foamed molded product may be deteriorated, and the bending strength may be insufficient. This is particularly noticeable during low pressure molding. .
本発明の発泡性スチレン系樹脂粒子に添加する発泡剤としては、沸点がスチレン系樹脂の軟化点以下であって、常圧でガス状もしくは液状の有機化合物が適しており、例えば、プロパン、ｎ−ブタン、イソブタン、ｎ−ペンタン、イソペンタン、ネオペンタン、シクロペンタン、シクロペンタジエン、ｎ−ヘキサン、石油エーテル等の炭化水素、ジメチルエーテル、ジエチルエーテル、ジプロピルエーテル、メチルエチルエーテル等の低沸点のエーテル化合物、炭酸ガス、窒素等の無機ガス等が用いられる。これらの発泡剤は、一種のみを使用してもよく、また、二種以上を併用してもよい。これらのうち、好ましい発泡剤は沸点が−４５〜４０℃の炭化水素であり、プロパン、ｎ−ブタン、イソブタン、ｎ−ペンタン、イソペンタン等が好ましい。 As a foaming agent to be added to the expandable styrene resin particles of the present invention, a gaseous or liquid organic compound having a boiling point below the softening point of the styrene resin and normal pressure is suitable. For example, propane, n -Hydrocarbons such as butane, isobutane, n-pentane, isopentane, neopentane, cyclopentane, cyclopentadiene, n-hexane, petroleum ether, low boiling point ether compounds such as dimethyl ether, diethyl ether, dipropyl ether, methyl ethyl ether, An inorganic gas such as carbon dioxide or nitrogen is used. These foaming agents may use only 1 type and may use 2 or more types together. Among these, preferable blowing agents are hydrocarbons having a boiling point of −45 to 40 ° C., and propane, n-butane, isobutane, n-pentane, isopentane and the like are preferable.
本発明の発泡性スチレン系樹脂粒子は、分子中に水酸基を有しない高級脂肪酸トリグリセライドの含有量を発泡性スチレン系樹脂粒子本体１００質量部に対して０．０５質量部未満とする必要がある。前記トリグリセライドは、発泡性スチレン系樹脂粒子の被覆材中に実質的に含まないことが望ましい。前記トリグリセライドを被覆材中に０．０５質量部以上含有すると、成形サイクルの短縮効果は得られるものの、製造される発泡成形品の表面光沢度及び曲げ強度が大きく低下してしまう。 In the expandable styrene resin particles of the present invention, the content of the higher fatty acid triglyceride having no hydroxyl group in the molecule needs to be less than 0.05 parts by mass with respect to 100 parts by mass of the expandable styrene resin particle main body. It is desirable that the triglyceride is not substantially contained in the covering material for the expandable styrene resin particles. When 0.05 parts by mass or more of the triglyceride is contained in the covering material, the effect of shortening the molding cycle can be obtained, but the surface glossiness and bending strength of the foamed molded article to be produced are greatly reduced.
本発明の発泡性スチレン系樹脂粒子において、トルエン及び臭素系難燃剤を含有せず、発泡助剤としてシクロヘキサンをスチレン系樹脂１００質量部に対し０．５〜１．５質量部の範囲で含むことが好ましい。ここで、臭素系難燃剤としては、例えば、ヘキサブロモシクロドデカン（ＨＢＣＤ）、テトラブロモブタン、ヘキサブロモシクロヘキサン等の臭素化脂肪族炭化水素系化合物、テトラブロモビスフェノールＡ、テトラブロモビスフェノールＦ、２，４，６−トリブロモフェノール等の臭素化フェノール類、テトラブロモビスフェノールＡ−ビス（２，３−ジブロモプロピルエーテル）、テトラブロモビスフェノールＡ−ジグリシジルエーテル等の臭素化フェノール誘導体が挙げられる。発泡性スチレン系樹脂粒子にトルエンを添加すると、発泡成形品の発泡粒子同士の融着率が低下する場合がある。発泡助剤としてシクロヘキサンを用いれば、前記融着率の低下が防止できる。また、発泡性スチレン系樹脂粒子に前記ＨＢＣＤ等の臭素系難燃剤を添加すると、気泡が微細化しやすく所望の気泡径に調整し難くなる。 The expandable styrene resin particles of the present invention do not contain toluene and bromine flame retardant, and contain cyclohexane as a foaming aid in the range of 0.5 to 1.5 parts by mass with respect to 100 parts by mass of the styrene resin. Is preferred. Here, examples of brominated flame retardants include brominated aliphatic hydrocarbon compounds such as hexabromocyclododecane (HBCD), tetrabromobutane and hexabromocyclohexane, tetrabromobisphenol A, tetrabromobisphenol F, 2, Examples thereof include brominated phenols such as 4,6-tribromophenol, and brominated phenol derivatives such as tetrabromobisphenol A-bis (2,3-dibromopropyl ether) and tetrabromobisphenol A-diglycidyl ether. When toluene is added to the expandable styrenic resin particles, the fusion rate between the expanded particles of the expanded molded product may be reduced. If cyclohexane is used as the foaming aid, the decrease in the fusion rate can be prevented. Moreover, when brominated flame retardants, such as said HBCD, are added to an expandable styrene-type resin particle, a bubble will become easy to refine | miniaturize and it will become difficult to adjust to a desired bubble diameter.
本発明の発泡性スチレン系樹脂粒子において、発泡時結合防止剤として無機粉体を添加しないことが望ましい。或いは、添加しても発泡性スチレン系樹脂粒子本体１００質量部に対して０．０５質量部未満とすることが望ましい。リン酸カルシウム、シリカ粉末等の無機粉体を被覆すると、前述したメチルフェニルシリコーンオイルを被覆しても、低圧蒸気成形時の融着率が悪化して、得られる発泡成形品の曲げ強度などの機械的性質が不十分となりやすい。発泡時結合防止剤としては、高級脂肪酸金属塩、特にステアリン酸亜鉛が好ましい。 In the expandable styrenic resin particles of the present invention, it is desirable not to add inorganic powder as a binding inhibitor during foaming. Or even if it adds, it is desirable to set it as less than 0.05 mass part with respect to 100 mass parts of expandable styrene resin particle main bodies. When inorganic powders such as calcium phosphate and silica powder are coated, the fusion rate during low-pressure steam molding deteriorates even when the above-mentioned methylphenyl silicone oil is coated. Properties tend to be insufficient. As the anti-foaming binder, a higher fatty acid metal salt, particularly zinc stearate, is preferred.
本発明の発泡性スチレン系樹脂粒子は、発泡剤と発泡助剤及び必要に応じて添加される添加剤を含む発泡性スチレン系樹脂粒子に、前記メチルフェニルシリコーンオイルと高級脂肪酸の金属塩とを、タンブラー、リボンブレンダー、ナウターミキサー等の混合機もしくは撹拌機を使用して、発泡性スチレン系樹脂粒子と混合して、その表面に被覆することによって製造することができる。被覆する順序は特に限定されないが、先にメチルフェニルシリコーンオイルを発泡性スチレン系樹脂粒子に被覆した後に、高級脂肪酸の金属塩を添加することが好ましい。この際、帯電防止剤等の公知の添加剤を同時に加えても良い。 The expandable styrenic resin particles of the present invention are obtained by adding the methylphenyl silicone oil and a metal salt of a higher fatty acid to the expandable styrenic resin particles containing a foaming agent, a foaming aid, and an additive that is added as necessary. Using a mixer or a stirrer such as a tumbler, ribbon blender, or Nauta mixer, the mixture can be mixed with the expandable styrenic resin particles and coated on the surface thereof. The order of coating is not particularly limited, but it is preferable to add a metal salt of a higher fatty acid after coating methylphenyl silicone oil on expandable styrene resin particles first. At this time, a known additive such as an antistatic agent may be added simultaneously.
本発明の発泡性スチレン系樹脂粒子は、発泡剤を含有するスチレン系樹脂からなり、嵩発泡倍数６０倍に発泡させたときの発泡粒子表層部の平均気泡径Ｄが、４０μｍ≦Ｄ≦１５０μｍの関係を満たす発泡性スチレン系樹脂粒子本体１００質量部に対して、２５℃での屈折率が１．４５以上であるメチルフェニルシリコーンオイル０．０１〜０．２質量部と、高級脂肪酸の金属塩０．０５〜０．２質量部とが粒子表面に被覆され、かつ、分子中に水酸基を有しない高級脂肪酸トリグリセライドの被覆量が０．０５質量部未満としたものなので、この発泡性スチレン系樹脂粒子を加熱して得られた予備発泡粒子を成形型のキャビティ内に充填し、型内発泡成形してスチレン系樹脂発泡成形品を得る際に、従来の型内発泡成形で使用するより低圧の蒸気でも発泡粒子同士を十分融着させることができ、低圧の蒸気で成形を行うことにより、成形時の冷却時間が短くなり、短い成形サイクルでも、十分な強度を持ち、表面光沢に優れた発泡成形品を得ることができる。 The expandable styrene resin particles of the present invention are made of a styrene resin containing a foaming agent, and the average cell diameter D of the expanded particle surface layer when expanded to a bulk expansion ratio of 60 times is 40 μm ≦ D ≦ 150 μm. 0.01 to 0.2 parts by mass of methylphenyl silicone oil having a refractive index at 25 ° C. of 1.45 or more with respect to 100 parts by mass of the expandable styrene resin particle main body satisfying the relationship, and a metal salt of a higher fatty acid Since the coating amount of the higher fatty acid triglyceride having 0.05 to 0.2 parts by mass on the particle surface and having no hydroxyl group in the molecule is less than 0.05 parts by mass, this expandable styrenic resin When the pre-expanded particles obtained by heating the particles are filled into the mold cavity and foam-molded in the mold to obtain a styrene resin foam-molded product, the pressure is lower than that used in conventional in-mold foam molding. Foamed particles can be sufficiently fused together with steam, and by molding with low-pressure steam, the cooling time during molding is shortened. Foam with sufficient strength and excellent surface gloss even in a short molding cycle A molded product can be obtained.
また本発明は、前述した本発明に係る発泡性スチレン系樹脂粒子を加熱して得られた予備発泡粒子を成形型のキャビティ内に充填し、型内発泡成形してスチレン系樹脂発泡成形品を得るスチレン系樹脂発泡成形品の製造方法を提供する。 The present invention also provides a pre-expanded particle obtained by heating the expandable styrenic resin particles according to the present invention described above, filled in a cavity of a molding die, and subjected to in-mold foam molding to obtain a styrene resin foam molded product. Provided is a method for producing a styrenic resin foam molded article.
本発明の製造方法において、発泡性スチレン系樹脂粒子の予備発泡を行う予備発泡装置や予備発泡条件は、従来の発泡性スチレン系樹脂粒子の予備発泡と同様に行うことができる。 In the production method of the present invention, the pre-foaming apparatus and pre-foaming conditions for pre-foaming the expandable styrene resin particles can be performed in the same manner as the pre-foaming of the conventional expandable styrene resin particles.
また本発明の製造方法において、予備発泡粒子を型内発泡成形する際に用いる成形装置、成形条件についても、従来の発泡性スチレン系樹脂粒子の型内発泡成形と同様に行うことができる。ただし、本発明の製造方法では、前述した本発明に係る発泡性スチレン系樹脂粒子を原料として用いることによって、通常の型内発泡成形（成形蒸気圧：０．０７ＭＰａＧ）よりも低圧の蒸気（成形蒸気圧：０．０６ＭＰａＧ〜０．０５ＭＰａＧ）で成形を行うことができ、成形時の冷却時間が短くなり、短い成形サイクルでも、十分な強度を持ち、表面光沢に優れた発泡成形品を得ることができる。
本発明の製造方法において、型内発泡成形する際の成形蒸気圧は０．０６ＭＰａＧ〜０．０５ＭＰａＧが好ましく、０．０５ＭＰａＧがより好ましい。
Further, in the production method of the present invention, the molding apparatus and molding conditions used when the pre-expanded particles are subjected to in-mold foam molding can be performed in the same manner as in the in-mold foam molding of conventional expandable styrene resin particles. However, in the production method of the present invention, by using the expandable styrene resin particles according to the present invention described above as a raw material, steam (molding) having a pressure lower than that of normal in-mold foam molding (molding vapor pressure: 0.07 MPaG). (Vapor pressure: 0.06 MPaG to 0.05 MPaG), cooling time during molding is shortened, and foam molded products having sufficient strength and excellent surface gloss are obtained even in a short molding cycle. Can do.
In the production method of the present invention, the molding vapor pressure at the time of in-mold foam molding is preferably 0.06 MPaG to 0.05 MPaG, more preferably 0.05 MPaG.
本発明の製造方法において、スチレン系樹脂発泡成形品の発泡倍数の適正範囲は、２０〜９０倍の範囲内であり、好ましくは３０〜８０倍の範囲内、より好ましくは５０〜７０倍の範囲内である。この発泡倍数が２０倍未満であると、成形サイクル短縮効果が小さく、９０倍を超えると、得られるスチレン系樹脂発泡成形品が収縮し易くなる。 In the production method of the present invention, the appropriate range of the expansion ratio of the styrene-based resin foam molded article is in the range of 20 to 90 times, preferably in the range of 30 to 80 times, more preferably in the range of 50 to 70 times. Is within. If the expansion ratio is less than 20 times, the effect of shortening the molding cycle is small, and if it exceeds 90 times, the resulting styrene resin foam-molded product tends to shrink.
本発明の製造方法によれば、前記発泡性スチレン系樹脂粒子を加熱して得られた予備発泡粒子を成形型のキャビティ内に充填し、蒸気圧０．０５ＭＰａＧの低圧蒸気成形により、発泡倍数６０倍のスチレン系樹脂発泡成形品を製造した際に、得られるスチレン系樹脂発泡成形品の曲げ強度（ＪＩＳ Ａ９５１１）が０．２５ＭＰａ以上のものを製造可能である。 According to the production method of the present invention, the pre-expanded particles obtained by heating the expandable styrenic resin particles are filled in a cavity of a molding die, and the expansion ratio is 60 by low pressure steam molding with a vapor pressure of 0.05 MPaG. When a double styrene resin foam molded article is produced, it is possible to produce a styrene resin foam molded article having a bending strength (JIS A9511) of 0.25 MPa or more.
また、本発明の製造方法によれば、前記発泡性スチレン系樹脂粒子を加熱して得られた予備発泡粒子を成形型のキャビティ内に充填し、蒸気圧０．０５ＭＰａＧの低圧蒸気成形により、発泡倍数６０倍のスチレン系樹脂発泡成形品を製造した際に、得られるスチレン系樹脂発泡成形品の表面光沢度（ＪＩＳ Ｚ８７４１、６０°／６０°）が２５以上のものを製造可能である。 In addition, according to the production method of the present invention, the pre-expanded particles obtained by heating the expandable styrene resin particles are filled in a cavity of a mold, and foaming is performed by low-pressure steam molding with a vapor pressure of 0.05 MPaG. When a styrene resin foam molded article having a multiple of 60 times is produced, it is possible to produce a styrene resin foam molded article having a surface glossiness (JIS Z8741, 60 ° / 60 °) of 25 or more.
本発明の発泡成形品は、成形サイクルを短縮して製造可能であることから、低コストで提供でき、外観的にも優れている。本発明の発泡成形品は、例えば、魚箱などの各種容器、建材用断熱ボード等の各種の用途に用いられる。 Since the foam-molded article of the present invention can be produced with a shortened molding cycle, it can be provided at low cost and is excellent in appearance. The foamed molded product of the present invention is used for various applications such as various containers such as fish boxes and heat insulating boards for building materials.
後述する実施例１〜７、比較例１〜１２に示した通り、発泡性スチレン系樹脂粒子をそれぞれ製造し、それぞれの発泡性スチレン系樹脂粒子を予備発泡−型内発泡成形してスチレン系樹脂発泡成形品を製造し、下記の各測定方法に従って、発泡粒子表層部の平均気泡径、成形品の融着率、成形品の曲げ強度、成形品の光沢度、最短冷却時間を測定し、水漏れ試験を行った。 As shown in Examples 1 to 7 and Comparative Examples 1 to 12, which will be described later, expandable styrene resin particles are produced, and the respective expandable styrene resin particles are pre-expanded and subjected to in-mold foam molding to produce styrene resins. Produce a foam molded product, and measure the average cell diameter of the foam particle surface layer part, the fusion rate of the molded product, the bending strength of the molded product, the glossiness of the molded product, and the minimum cooling time according to the following measurement methods. A leak test was performed.
＜嵩発泡倍数の測定方法＞
嵩発泡倍数は予備発泡粒子（予備発泡後、２３℃で２４時間熟成させたもの）を試料としてメスシリンダー（例３０００ｍｌ容量）内に自然落下させたのち、メスシリンダーの底をたたいて試料容積を一定にさせ、その容積と質量を測定し次式により算出した。質量は０．１ｇ単位で測定し、樹脂比重はスチレン系樹脂の場合１．０とした。嵩発泡倍数は小数点以下１桁目を四捨五入した。
嵩発泡倍数（倍）＝メスシリンダー中の試料容積（ｍｌ）／試料質量（ｇ）×樹脂比重
＜発泡倍数の測定方法＞
発泡倍数は発泡成形品（成形後、４０℃で２０時間以上乾燥させたもの）から切り出した試験片（例７５×３００×３５ｍｍ）の寸法と質量をそれぞれ有効数字３桁以上になるように測定し、次式により算出した。樹脂比重は、スチレン系樹脂の場合１．０とした。発泡倍数は小数点以下１桁目を四捨五入した。
発泡倍数（倍）＝試験片体積（ｃｍ３）／試験片質量（ｇ）×樹脂比重
＜発泡粒子表層部の平均気泡径測定方法＞
嵩発泡倍数６０倍に発泡させた発泡粒子の中から、任意に選択した１０個について、剃刀刃を用いて、それぞれ発泡粒子の中心付近を通る平面で二等分し、その一方の切断面を走査型電子顕微鏡（日立製作所製Ｓ−３０００Ｎ）を用いて２５〜２００倍に拡大撮影した画像を作成した。
次に、発泡粒子切断面の画像上に、発泡粒子の中心から半径の９０％に相当する距離を半径とする円を描き、この円の外側に存在する気泡を発泡粒子表層部の気泡と定義し、この気泡についてＡＳＴＭ Ｄ２８４２−６９の試験方法に準拠して測定した。すなわち、各画像について円の外側の任意の部分に長さ６０ｍｍの直線を引き、この直線上にある気泡の個数を数え、次式によりこの気泡の平均弦長（ｔ）を算出した。なお、直線の長さが６０ｍｍに満たない場合は、３０ｍｍ又は２０ｍｍの気泡数を数え６０ｍｍ分の気泡数に換算した。
平均弦長 ｔ（μｍ）＝（60×1000）／（気泡数×画像の拡大倍率）
次に次式により、この気泡の平均気泡径（Ｄ）を算出した。
平均気泡径 Ｄ（μｍ）＝ｔ／０．６１６
各画像について、円の外側の任意の６カ所について計測し、計１０画像分の平均値を平均気泡径とした。
<Measurement method of bulk expansion ratio>
The bulk expansion ratio was determined by dropping the pre-expanded particles (pre-expanded and aged at 23 ° C. for 24 hours) into a graduated cylinder (example: 3000 ml capacity) and then tapping the bottom of the graduated cylinder. The volume and mass were measured and the following formula was calculated. The mass was measured in units of 0.1 g, and the specific gravity of the resin was 1.0 in the case of styrene resin. The bulk expansion factor was rounded to the first decimal place.
Bulk expansion ratio (times) = sample volume (ml) / sample mass (g) in the graduated cylinder x resin specific gravity <Measurement method of expansion ratio>
The expansion ratio was measured so that the size and mass of a test piece (example 75 × 300 × 35 mm) cut out from a foamed molded product (after molding and dried at 40 ° C. for 20 hours or more) were each at least 3 significant figures. And calculated by the following formula. The specific gravity of the resin was 1.0 in the case of styrene resin. The foaming multiple was rounded off to the first decimal place.
Foaming multiple (times) = test piece volume (cm 3 ) / test piece mass (g) × resin specific gravity <average cell diameter measurement method of foamed particle surface layer>
About 10 arbitrarily selected foam particles expanded to a bulk expansion ratio of 60 times, using a razor blade, each is divided into two equal parts by a plane passing near the center of the foam particles, and one of the cut surfaces is divided. Using a scanning electron microscope (S-3000N manufactured by Hitachi, Ltd.), an image that was magnified 25 to 200 times was created.
Next, a circle with a radius corresponding to 90% of the radius from the center of the foam particle is drawn on the image of the cut surface of the foam particle, and bubbles existing outside the circle are defined as bubbles on the surface layer of the foam particle. These bubbles were measured in accordance with the test method of ASTM D2842-69. That is, for each image, a straight line having a length of 60 mm was drawn on an arbitrary portion outside the circle, the number of bubbles on the straight line was counted, and the average chord length (t) of the bubbles was calculated by the following equation. When the length of the straight line was less than 60 mm, the number of bubbles of 30 mm or 20 mm was counted and converted to the number of bubbles of 60 mm.
Average chord length t (μm) = (60 × 1000) / (number of bubbles × magnification of image)
Next, the average bubble diameter (D) of the bubbles was calculated by the following formula.
Average bubble diameter D (μm) = t / 0.616
About each image, it measured about arbitrary 6 places outside a circle, and made the average value for a total of 10 images the average bubble diameter.
＜融着率の測定方法＞
幅３００ｍｍ、長さ４００ｍｍ、厚み３５ｍｍの平板形状の発泡成形品の表面に、一対の長辺の中心同士を結ぶ直線に沿ってカッターナイフで深さ約２ｍｍの切り込み線を入れた後、この切り込み線に沿って発泡成形品を手で二分割し、その破断面における発泡粒子について、１００〜１５０個の任意の範囲について粒子内で破断している粒子の数（ａ）と粒子どうしの界面で破断している粒子の数（ｂ）とを数え、式［（a）／（（a）十（b））］×100に代入して得られた値を融着率（％）とした。
融着性の評価として、融着率７０％以上を良好（○）、融着率７０％未満を不良（×）とした。
<Measurement method of fusion rate>
After making a cut line with a depth of about 2 mm with a cutter knife along the straight line connecting the centers of a pair of long sides on the surface of a flat foam molded product having a width of 300 mm, a length of 400 mm and a thickness of 35 mm, this cut The foamed molded product is divided into two along the line by hand, and the foamed particles in the fracture surface at the interface between the number of particles (a) broken within the particles in an arbitrary range of 100 to 150 and between the particles The number of broken particles (b) was counted, and the value obtained by substituting into the formula [(a) / ((a) tens (b))] × 100 was defined as the fusion rate (%).
As evaluation of the fusing property, a fusing rate of 70% or more was judged as good (◯), and a fusing rate of less than 70% was judged as poor (x).
＜曲げ強度＞
発泡倍数６０倍の発泡成形品を作製し、最大曲げ強さはＪＩＳ Ａ９５１１：１９９９「発泡プラスチック保温材」記載の方法に準じて測定した。すなわち、テンシロン万能試験機ＵＣＴ−１０Ｔ（オリエンテック社製）を用い、試験体サイズは７５×３００×３５ｍｍで圧縮速度を１０ｍｍ／ｍｉｎ、先端治具は加圧くさび１０Ｒ、支持台１０Ｒで、支点間距離は２００ｍｍとして測定した。
測定方法試験装置：テンシロン万能試験機ＵＣＴ−１０Ｔ（オリエンテック社製）。
試験片：７５×３００×３５ｍｍ。試験片の数は３個とする。
試験速度：１０ｍｍ／ｍｉｎ。
先端治具：加圧くさび…１０Ｒ、支持台…１０Ｒ。
支点間距離：２００ｍｍ。ＪＩＳ Ａ９５１１規格に準じて、発泡成形品の曲げ強度を測定した。
曲げ強度測定に用いた試験片は、実施例・比較例で得られた成形品（３００×４００×３５ｍｍ）から切り出して作製した。成形圧（水蒸気吹き込みゲージ圧）を０．０７ＭＰａＧ、０．０６ＭＰａＧ及び０．０５ＭＰａＧとした場合のそれぞれの発泡成形品の曲げ強度を測定し、以下の基準で評価した
○：０．２９ＭＰａ以上
△：０．２５ＭＰａ以上０．２９ＭＰａ未満
×：０．２５ＭＰａ未満
<Bending strength>
A foamed molded article having a foaming ratio of 60 times was prepared, and the maximum bending strength was measured according to the method described in JIS A9511: 1999 “Foamed plastic heat insulating material”. That is, using Tensilon universal testing machine UCT-10T (Orientec Co., Ltd.), the specimen size is 75 x 300 x 35 mm, the compression speed is 10 mm / min, the tip jig is the pressure wedge 10R, and the support base 10R, the fulcrum The distance was measured as 200 mm.
Measuring method test apparatus: Tensilon universal testing machine UCT-10T (Orientec Co., Ltd.).
Test piece: 75 × 300 × 35 mm. The number of test pieces shall be three.
Test speed: 10 mm / min.
Tip jig: pressure wedge 10R, support base 10R.
Distance between fulcrums: 200 mm. The bending strength of the foamed molded product was measured according to JIS A9511 standard.
The test piece used for the bending strength measurement was cut out from the molded product (300 × 400 × 35 mm) obtained in Examples and Comparative Examples. The bending strength of each foamed molded article when the molding pressure (water vapor blowing gauge pressure) was 0.07 MPaG, 0.06 MPaG, and 0.05 MPaG was measured, and evaluated according to the following criteria: ○: 0.29 MPa or more Δ: 0.25 MPa or more and less than 0.29 MPa ×: less than 0.25 MPa
＜成形品の光沢度の評価＞
完全に平滑な測定面を得るために、成形用型窩の移動型の表面に、顕微鏡用スライドグラス（松浪硝子工業株式会社製、レギュラースライドグラス、長さ７６ｍｍ、幅２６ｍｍ）５枚を市販の両面テープを用いて、型窩の蒸気導入スリットを避けた位置に貼り付けて、実施例・比較例に示す成形蒸気圧０．０５ＭＰａＧの成形条件にて成形した。得られた成形品を常温で約７０時間乾燥させてから、ピンセットを用いて慎重にスライドグラスを剥がし、光沢度測定用の完全に平滑な成形品表面を得た。次に、光沢計（ミノルタ株式会社製ＧＭ−０６０）を用いて、この光沢度測定用部位の任意の１５点について、ＪＩＳ Ｚ８７４１に基づく６０°／６０°の光沢度を測定し、その平均値を光沢度とした。
光沢度は次の基準により評価した。
○：３０以上
△：２５以上３０未満
×：２５未満
<Evaluation of gloss of molded products>
In order to obtain a completely smooth measurement surface, five microscope slide glasses (manufactured by Matsunami Glass Industrial Co., Ltd., regular slide glass, length 76 mm, width 26 mm) are commercially available on the movable surface of the molding cavity. Using a double-sided tape, it was affixed at a position avoiding the steam introduction slit of the mold cavity, and was molded under the molding conditions of molding vapor pressure of 0.05 MPaG shown in Examples and Comparative Examples. The obtained molded product was dried at room temperature for about 70 hours, and then the slide glass was carefully peeled off using tweezers to obtain a completely smooth molded product surface for gloss measurement. Next, using a gloss meter (GM-060 manufactured by Minolta Co., Ltd.), the glossiness of 60 ° / 60 ° based on JIS Z8741 is measured for any 15 points of this glossiness measurement site, and the average value thereof is measured. Was the glossiness.
The glossiness was evaluated according to the following criteria.
○: 30 or more Δ: 25 or more and less than 30 ×: less than 25
＜最短冷却時間＞
３成形条件中、８０％以上の融着率が得られる最も短い冷却時間を最短冷却時間とした。
<Minimum cooling time>
Among the three molding conditions, the shortest cooling time at which a fusion rate of 80% or more was obtained was taken as the shortest cooling time.
＜成形品の水漏れ試験＞
成形機の型窩を、外寸３００×４００×１００ｍｍで２５ｍｍの均一な厚みを有する箱形の成形品（内寸２５０×３５０×７５ｍｍ）が得られるものに取り替えて、成形蒸気圧０．０７ＭＰａＧの前述成形条件にて成形して、箱形の成形品を得た。得られた成形品を常温で６時間放置した後、新聞紙の上に成形品を置き、この成形品に水溶性の赤インクで着色した水道水５リットルを入れて常温で更に７２時間放置した後、成形品を取り除いて新聞紙を観察した。
成形品の水漏れは次の基準で評価した。
○：全く漏れていない
△：新聞紙に点状に僅かに着色が見られる
×：新聞紙に濡れており、全体が着色している
<Water leakage test of molded products>
Replace the mold cavity of the molding machine with an outer dimension of 300 x 400 x 100 mm and a box-shaped molded product (inner dimension of 250 x 350 x 75 mm) with a uniform thickness of 25 mm, and a molding vapor pressure of 0.07 MPaG The above-mentioned molding conditions were used to obtain a box-shaped molded product. After the molded product thus obtained is left at room temperature for 6 hours, the molded product is placed on a newspaper, and 5 liters of tap water colored with water-soluble red ink is added to the molded product and left at room temperature for a further 72 hours. The molded article was removed and the newspaper was observed.
The leakage of the molded product was evaluated according to the following criteria.
○: No leakage at all △: Slightly colored spotted on newspapers ×: Wet on newspapers, the whole is colored
［実施例１］
撹拌機を備えた内容積５２リットルの反応器に、蒸留水１８ｋｇ、ピロリン酸マグネシウム６５ｇ、ドデシルベンゼンスルホン酸ナトリウム２．５ｇを入れ、粒子径が約０．６ｍｍで重量平均分子量が３０万のスチレン樹脂種粒子（積水化成品工業株式会社製、ＳＳ−１５２）５．０ｋｇを加えて撹拌し懸濁させた。
次いで予め用意した蒸留水１５００ｇ、ピロリン酸マグネシウム５．０ｇ、ドデシルベンゼンスルホン酸ナトリウム１．０ｇの分散液に、重合開始剤としてベンゾイルパーオキサイド５０．７ｇ及びｔ−ブチルパーオキシベンゾエート１６．９ｇ、気泡調整剤としてジドデシル３，３’−チオジプロピオネート０．３４ｇをスチレン２１６０ｇに溶解して添加し、ホモミキサーにかけて調製した懸濁液を７１℃に保持した反応器に加えた。
撹拌しながら７１℃で１時間保持し、スチレン樹脂種粒子に重合開始剤と気泡調整剤を吸収させた後、反応器内にスチレンを４９２０ｇ／ｈｒの速度で連続的に３．０時間供給するとともに、スチレン供給終了時に懸濁液が１０５℃となるように反応器を連続的に昇温した。引き続き１２０℃まで昇温して３０分保持した後、蒸留水２０００ｇにピロリン酸マグネシウム６．５ｇ、ドデシルベゼンスルホン酸ナトリウム０．６ｇを加えた分散液に、発泡助剤としてシクロヘキサン１７５．３ｇ、ジイソブチルアジペート（ＤＩＢＡ）１５３．４ｇを加えてホモミキサーにかけた懸濁液を反応器内に圧入した。その後、１００℃まで冷却して工業用ブタン（イソブタン／ノルマルブタン＝３５／６５）１９７５ｇを圧入して１００℃で３時間保持した後、２０℃まで冷却して取り出し、洗浄、脱水、乾燥した。さらに発泡後の気泡径が完全に安定するまで１８℃で５日間熟成させて、粒子径約１．０ｍｍの発泡性スチレン樹脂粒子を得た。この発泡性スチレン樹脂粒子を嵩発泡倍数６０倍に発泡した発泡粒子表層部の平均気泡径は７１μｍであった。
この発泡性スチレン樹脂粒子１０ｋｇに対して、ステアリン酸亜鉛（大日化学工業株式会社製ダイワックスＺＦ）１３．０ｇ、メチルフェニルシリコーンオイル（ＧＥ東芝シリコーン株式会社製ＴＳＦ４３００、２５℃における粘度１４０ｍｍ２／ｓ、屈折率１．４９８）５．０ｇを内容積約３０リットルのタンブラーミキサーを用いて、毎分３０回転で約１５分間混合して、樹脂粒子の表面に被覆した。
得られた発泡性スチレン樹脂粒子を内容積約４０リットルの小型バッチ式予備発泡機を用いて、常圧下で水蒸気により加熱し、嵩発泡倍数６０倍に予備発泡した。得られた予備発泡粒子を目開き１０ｍｍの篩に通して、篩上に残った発泡時結合粒子の質量を、発泡に用いた発泡性樹脂粒子の質量で除して予備発泡時結合量を算出した。結合量は０．３％であった。
結合粒子を取り除いた予備発泡粒子を網袋に入れ、２３℃で２４時間熟成させた後、３００×４００×３５ｍｍの型窩を取り付けた発泡成形機（株式会社積水工機製作所製ＡＣＥ−３ＳＰ）を用いて、下記３条件で成形を行った。水冷工程終了後から取出設定面圧０．０２ＭＰａになるまでの放冷時間を冷却時間とした。冷却時間は、１条件について各３枚成形してその平均値をとった。
成形条件（ＡＣＥ−３ＳＰ ＱＳ成形モード）
成形蒸気圧 ３条件（ゲージ圧０．０７、０．０６、０．０５ＭＰａ）
金型加熱３秒
一方加熱（圧力設定０．０３ＭＰａ）
逆一方加熱２秒
両面加熱１０秒
水冷５秒
取出設定面圧０．０２ＭＰａ
得られた幅３００ｍｍ、長さ４００ｍｍ、厚み３５ｍｍの成形品を、４０℃の乾燥室内で２０時間乾燥させ発泡倍数６０倍の発泡成形品を得て、成形品の融着率、曲げ強度、光沢度等を測定した。結果を表１，２に示す。
[Example 1]
Styrene having a particle size of about 0.6 mm and a weight average molecular weight of 300,000 is placed in a reactor having an internal volume of 52 liters equipped with a stirrer and 18 kg of distilled water, 65 g of magnesium pyrophosphate and 2.5 g of sodium dodecylbenzenesulfonate. 5.0 kg of resin seed particles (SS-152, manufactured by Sekisui Plastics Co., Ltd.) were added and suspended by stirring.
Next, in a dispersion of 1500 g of distilled water prepared in advance, 5.0 g of magnesium pyrophosphate and 1.0 g of sodium dodecylbenzenesulfonate, 50.7 g of benzoyl peroxide and 16.9 g of t-butylperoxybenzoate as a polymerization initiator, air bubbles As a regulator, 0.34 g of didodecyl 3,3′-thiodipropionate was dissolved in 2160 g of styrene and added, and the suspension prepared by applying a homomixer was added to a reactor maintained at 71 ° C.
The mixture is held at 71 ° C. for 1 hour with stirring, and after the styrene resin seed particles have absorbed the polymerization initiator and the air conditioner, styrene is continuously fed into the reactor at a rate of 4920 g / hr for 3.0 hours. At the same time, the temperature of the reactor was continuously raised so that the suspension became 105 ° C. at the end of the styrene supply. Subsequently, the temperature was raised to 120 ° C. and held for 30 minutes, and then 175.3 g of cyclohexane as a foaming aid was added to a dispersion obtained by adding 6.5 g of magnesium pyrophosphate and 0.6 g of sodium dodecylbezenesulfonate to 2000 g of distilled water. A suspension obtained by adding 153.4 g of diisobutyl adipate (DIBA) and applying it to a homomixer was pressed into the reactor. Then, after cooling to 100 ° C., 1975 g of industrial butane (isobutane / normal butane = 35/65) was injected and held at 100 ° C. for 3 hours, then cooled to 20 ° C., taken out, washed, dehydrated and dried. Further, the foamed styrene resin particles having a particle diameter of about 1.0 mm were obtained by aging at 18 ° C. for 5 days until the bubble diameter after foaming was completely stabilized. The average cell diameter of the surface layer of the expanded particles obtained by expanding the expandable styrene resin particles to a bulk expansion ratio of 60 times was 71 μm.
For this expandable styrene resin particles 10 kg, zinc stearate (Dainichi Kagaku Kogyo Co., Ltd. die wax ZF) 13.0 g, methylphenyl silicone oil (GE Toshiba Silicone Co., Ltd. TSF4300,25 viscosity at ° C. 140 mm 2 / s, refractive index 1.498) 5.0 g was mixed for about 15 minutes at 30 revolutions per minute using a tumbler mixer having an internal volume of about 30 liters to coat the surface of the resin particles.
The obtained expandable styrene resin particles were heated with steam under normal pressure using a small batch type pre-foaming machine having an internal volume of about 40 liters, and pre-foamed to a bulk foaming ratio of 60 times. The obtained pre-foamed particles are passed through a sieve having an opening of 10 mm, and the mass of the bonded particles remaining on the sieve is divided by the mass of the foamable resin particles used for foaming to calculate the pre-foamed bonded amount. did. The amount of binding was 0.3%.
The pre-foamed particles from which the binding particles have been removed are placed in a net bag and aged at 23 ° C. for 24 hours, and then a foam molding machine with a 300 × 400 × 35 mm mold cavity (ACE-3SP, manufactured by Sekisui Koki Co., Ltd.) Was molded under the following three conditions. The cooling time was defined as the cooling time from the end of the water cooling process until the extraction set surface pressure reached 0.02 MPa. For the cooling time, three sheets were molded for one condition and the average value was taken.
Molding conditions (ACE-3SP QS molding mode)
Molding vapor pressure 3 conditions (gauge pressure 0.07, 0.06, 0.05 MPa)
Mold heating 3 seconds One side heating (pressure setting 0.03MPa)
Reverse one heating 2 seconds Double-side heating 10 seconds Water cooling 5 seconds Extraction set surface pressure 0.02 MPa
The obtained molded product having a width of 300 mm, a length of 400 mm, and a thickness of 35 mm is dried in a drying chamber at 40 ° C. for 20 hours to obtain a foamed molded product having a expansion ratio of 60 times, and the fusion rate, bending strength, and gloss of the molded product are obtained. The degree was measured. The results are shown in Tables 1 and 2.
［実施例２］
メチルフェニルシリコーンオイルの被覆量を５．０ｇから１．０ｇに変えた以外は、実施例１と同様の操作を行い同様に評価した。結果を表１，２に示す。
[Example 2]
The same operation as in Example 1 was performed, except that the coating amount of methylphenyl silicone oil was changed from 5.0 g to 1.0 g. The results are shown in Tables 1 and 2.
［実施例３］
メチルフェニルシリコーンオイルの被覆量を５．０ｇから１５．０ｇに変えた以外は、実施例１と同様の操作を行い同様に評価した。結果を表１，２に示す。
[Example 3]
The same operation as in Example 1 was performed, except that the coating amount of methylphenyl silicone oil was changed from 5.0 g to 15.0 g. The results are shown in Tables 1 and 2.
［実施例４］
被覆するメチルフェニルシリコーンオイルを信越化学工業株式会社製ＫＦ−５６（２５℃における粘度１５ｍｍ２／ｓ、屈折率１．５００）に変えた以外は、実施例１と同様の操作を行い同様に評価した。結果を表１，２に示す。
[Example 4]
The same operation as in Example 1 was performed, except that the methylphenyl silicone oil to be coated was changed to KF-56 manufactured by Shin-Etsu Chemical Co., Ltd. (viscosity 15 mm 2 / s at 25 ° C., refractive index 1.500) and evaluated in the same manner. did. The results are shown in Tables 1 and 2.
［実施例５］
被覆するメチルフェニルシリコーンオイルを東レダウコーニング株式会社製ＳＨ７１０（２５℃における粘度５００ｍｍ２／ｓ、屈折率１．５３３）に変えた以外は、実施例１と同様の操作を行い同様に評価した。結果を表１，２に示す。
[Example 5]
The same operations as in Example 1 were carried out and evaluated in the same manner except that the methylphenyl silicone oil to be coated was changed to SH710 manufactured by Toray Dow Corning Co., Ltd. (viscosity 500 mm 2 / s at 25 ° C., refractive index 1.533). The results are shown in Tables 1 and 2.
［実施例６］
撹拌機を備えた内容積５２リットルの反応器に、蒸留水１８ｋｇ、ピロリン酸マグネシウム６５ｇ、ドデシルベンゼンスルホン酸ナトリウム２．５ｇを入れ、実施例１で用いたスチレン樹脂種粒子５．０ｋｇを加えて撹拌し懸濁させた。
次いで予め用意した蒸留水１５００ｇ、ピロリン酸マグネシウム５．０ｇ、ドデシルベンゼンスルホン酸ナトリウム１．０ｇの分散液に、重合開始剤としてベンゾイルパーオキサイド４７．３ｇ及びｔ−ブチルパーオキシベンゾエート１６．９ｇ、気泡調整剤としてジドデシル３，３’−チオジプロピオネート０．５１ｇをスチレン２１６０ｇに溶解して添加し、ホモミキサーにかけて調製した懸濁液を６９℃に保持した反応器に加えた。
撹拌しながら６９℃で１時間保持し、スチレン樹脂種粒子に重合開始剤と気泡調整剤を吸収させた後、反応器内にスチレンを４９２０ｇ／ｈｒの速度で連続的に３．０時間供給するとともに、スチレン供給終了時に懸濁液が１０５℃となるように反応器を連続的に昇温した。引き続き１２０℃まで昇温して３０分保持した後、蒸留水２０００ｇにピロリン酸マグネシウム６．５ｇ、ドデシルベゼンスルホン酸ナトリウム０．６ｇを加えた分散液に、発泡助剤としてシクロヘキサン１７５．３ｇ、ジイソブチルアジペート（ＤＩＢＡ）１５３．４ｇを加えてホモミキサーにかけた懸濁液を反応器内に圧入した。その後、１００℃まで冷却して工業用ブタン（イソブタン／ノルマルブタン＝３５／６５）１９７５ｇを圧入して１００℃で３時間保持した後、２０℃まで冷却して取り出し、洗浄、脱水、乾燥した。さらに発泡後の気泡径が完全に安定するまで１８℃で５日間熟成させて、粒子径約１．０ｍｍの発泡性スチレン樹脂粒子を得た。この発泡性スチレン樹脂粒子を嵩発泡倍数６０倍に発泡した発泡粒子表層部の平均気泡径は５３μｍであった。
この発泡性スチレン樹脂粒子について、実施例１と同様の操作を行い同様に評価した。結果を表１，２に示す。
[Example 6]
Into a reactor having an internal volume of 52 liters equipped with a stirrer, 18 kg of distilled water, 65 g of magnesium pyrophosphate and 2.5 g of sodium dodecylbenzenesulfonate were added, and 5.0 kg of the styrene resin seed particles used in Example 1 were added. Stir and suspend.
Next, in a dispersion of 1500 g of distilled water prepared in advance, 5.0 g of magnesium pyrophosphate and 1.0 g of sodium dodecylbenzenesulfonate, 47.3 g of benzoyl peroxide and 16.9 g of t-butylperoxybenzoate as a polymerization initiator, bubbles As a modifier, 0.51 g of didodecyl 3,3′-thiodipropionate was dissolved in 2160 g of styrene and added, and the suspension prepared by applying a homomixer was added to a reactor maintained at 69 ° C.
The mixture is held at 69 ° C. for 1 hour with stirring, and after the styrene resin seed particles have absorbed the polymerization initiator and the air conditioner, styrene is continuously fed into the reactor at a rate of 4920 g / hr for 3.0 hours. At the same time, the temperature of the reactor was continuously raised so that the suspension became 105 ° C. at the end of the styrene supply. Subsequently, the temperature was raised to 120 ° C. and held for 30 minutes, and then 175.3 g of cyclohexane as a foaming aid was added to a dispersion obtained by adding 6.5 g of magnesium pyrophosphate and 0.6 g of sodium dodecylbezenesulfonate to 2000 g of distilled water. A suspension obtained by adding 153.4 g of diisobutyl adipate (DIBA) and applying it to a homomixer was pressed into the reactor. Then, after cooling to 100 ° C., 1975 g of industrial butane (isobutane / normal butane = 35/65) was injected and held at 100 ° C. for 3 hours, then cooled to 20 ° C., taken out, washed, dehydrated and dried. Further, the foamed styrene resin particles having a particle diameter of about 1.0 mm were obtained by aging at 18 ° C. for 5 days until the bubble diameter after foaming was completely stabilized. The average cell diameter of the surface layer of the expanded particles obtained by expanding the expandable styrene resin particles to a bulk expansion ratio of 60 times was 53 μm.
About this expandable styrene resin particle, operation similar to Example 1 was performed and evaluated similarly. The results are shown in Tables 1 and 2.
［実施例７］
撹拌機を備えた内容積５２リットルの反応器に、蒸留水１８ｋｇ、ピロリン酸マグネシウム６５ｇ、ドデシルベンゼンスルホン酸ナトリウム２．５ｇを入れ、実施例１で用いたスチレン樹脂種粒子５．０ｋｇを加えて撹拌し懸濁させた。
次いで予め用意した蒸留水１５００ｇ、ピロリン酸マグネシウム５．０ｇ、ドデシルベンゼンスルホン酸ナトリウム１．０ｇの分散液に、重合開始剤としてベンゾイルパーオキサイド６７．６ｇ及びｔ−ブチルパーオキシベンゾエート１６．９ｇ、気泡調整剤としてジドデシル３，３’−チオジプロピオネート０．１７ｇをスチレン２１６０ｇに溶解して添加し、ホモミキサーにかけて調製した懸濁液を７５℃に保持した反応器に加えた。
撹拌しながら７５℃で１時間保持し、スチレン樹脂種粒子に重合開始剤と気泡調整剤を吸収させた後、反応器内にスチレンを５９００ｇ／ｈｒの速度で連続的に２．５時間供給するとともに、スチレン供給終了時に懸濁液が１０５℃となるように反応器を連続的に昇温した。引き続き１２０℃まで昇温して３０分保持した後、蒸留水２０００ｇにピロリン酸マグネシウム６．５ｇ、ドデシルベゼンスルホン酸ナトリウム０．６ｇを加えた分散液に、発泡助剤としてシクロヘキサン１７５．３ｇ、ジイソブチルアジペート（ＤＩＢＡ）１５３．４ｇを加えてホモミキサーにかけた懸濁液を反応器内に圧入した。その後、１００℃まで冷却して工業用ブタン（イソブタン／ノルマルブタン＝３５／６５）１９７５ｇを圧入して１００℃で３時間保持した後、２０℃まで冷却して取り出し、洗浄、脱水、乾燥した。さらに発泡後の気泡径が完全に安定するまで１８℃で５日間熟成させて、粒子径約１．０ｍｍの発泡性スチレン樹脂粒子を得た。この発泡性スチレン樹脂粒子を嵩発泡倍数６０倍に発泡した発泡粒子表層部の平均気泡径は１２６μｍであった。
この発泡性スチレン樹脂粒子について、実施例１と同様の操作を行い同様に評価した。結果を表１，２に示す。
[Example 7]
Into a reactor having an internal volume of 52 liters equipped with a stirrer, 18 kg of distilled water, 65 g of magnesium pyrophosphate and 2.5 g of sodium dodecylbenzenesulfonate were added, and 5.0 kg of the styrene resin seed particles used in Example 1 were added. Stir and suspend.
Next, in a dispersion of 1500 g of distilled water prepared in advance, 5.0 g of magnesium pyrophosphate and 1.0 g of sodium dodecylbenzenesulfonate, 67.6 g of benzoyl peroxide and 16.9 g of t-butylperoxybenzoate as a polymerization initiator, bubbles As a conditioner, 0.17 g of didodecyl 3,3′-thiodipropionate was dissolved in 2160 g of styrene and added, and the suspension prepared by applying a homomixer was added to a reactor maintained at 75 ° C.
The mixture is held at 75 ° C. for 1 hour with stirring, and after the styrene resin seed particles have absorbed the polymerization initiator and the bubble regulator, styrene is continuously fed into the reactor at a rate of 5900 g / hr for 2.5 hours. At the same time, the temperature of the reactor was continuously raised so that the suspension became 105 ° C. at the end of the styrene supply. Subsequently, the temperature was raised to 120 ° C. and held for 30 minutes, and then 175.3 g of cyclohexane as a foaming aid was added to a dispersion obtained by adding 6.5 g of magnesium pyrophosphate and 0.6 g of sodium dodecylbezenesulfonate to 2000 g of distilled water. A suspension obtained by adding 153.4 g of diisobutyl adipate (DIBA) and applying it to a homomixer was pressed into the reactor. Then, after cooling to 100 ° C., 1975 g of industrial butane (isobutane / normal butane = 35/65) was injected and held at 100 ° C. for 3 hours, then cooled to 20 ° C., taken out, washed, dehydrated and dried. Further, the foamed styrene resin particles having a particle diameter of about 1.0 mm were obtained by aging at 18 ° C. for 5 days until the bubble diameter after foaming was completely stabilized. The average cell diameter of the surface layer of the expanded particles obtained by expanding the expandable styrene resin particles to a bulk expansion ratio of 60 times was 126 μm.
About this expandable styrene resin particle, operation similar to Example 1 was performed and evaluated similarly. The results are shown in Tables 1 and 2.
［比較例１］
メチルフェニルシリコーンオイルを被覆しなかった以外は、実施例１と同様の操作を行い同様に評価した。結果を表１，２に示す。
[Comparative Example 1]
The same operation as in Example 1 was performed, except that methylphenyl silicone oil was not coated, and the same evaluation was performed. The results are shown in Tables 1 and 2.
［比較例２］
メチルフェニルシリコーンオイルを被覆しなかった以外は、実施例７と同様の操作を行い同様に評価した。結果を表１，２に示す。
[Comparative Example 2]
The same operation as in Example 7 was performed, except that methylphenyl silicone oil was not coated, and the same evaluation was performed. The results are shown in Tables 1 and 2.
［比較例３］
メチルフェニルシリコーンオイルの被覆量を５．０ｇから０．２ｇに変えた以外は、実施例１と同様の操作を行い同様に評価した。結果を表１，２に示す。
[Comparative Example 3]
The same operation as in Example 1 was performed, except that the coating amount of methylphenyl silicone oil was changed from 5.0 g to 0.2 g. The results are shown in Tables 1 and 2.
［比較例４］
メチルフェニルシリコーンオイルの被覆量を５．０ｇから５０．０ｇに変えた以外は、実施例１と同様の操作を行い発泡性スチレン樹脂粒子に被覆した結果、ベタツキが大きく樹脂粒子の流動性が非常に悪くなったため、これについては発泡、成形評価を取りやめた。
[Comparative Example 4]
Except that the coating amount of methylphenyl silicone oil was changed from 5.0 g to 50.0 g, the same operation as in Example 1 was carried out to coat the expandable styrene resin particles. As a result, the stickiness was large and the fluidity of the resin particles was extremely high. As a result, the evaluation of foaming and molding was canceled.
［比較例５］
メチルフェニルシリコーンオイルを、ジメチルシリコーンオイル（信越化学工業株式会社製ＫＦ−９６−１００ｃｓ、２５℃における粘度１００ｍｍ２／ｓ、屈折率１．４０３）に代えた以外は、実施例１と同様の操作を行い同様に評価した。結果を表１，２に示す。
[Comparative Example 5]
The same operation as in Example 1 except that methylphenyl silicone oil was replaced with dimethyl silicone oil (KF-96-100cs, manufactured by Shin-Etsu Chemical Co., Ltd., viscosity 100 mm 2 / s at 25 ° C., refractive index 1.403). And evaluated in the same manner. The results are shown in Tables 1 and 2.
［比較例６］
メチルフェニルシリコーンオイルを、屈折率の低いもの（東レダウコーニング製ＳＨ５１０、２５℃における粘度１００ｍｍ２／ｓ、屈折率１．４２５）に代えた以外は、実施例１と同様の操作を行い同様に評価した。結果を表１，２に示す。
[Comparative Example 6]
The same operation as in Example 1 was performed except that methylphenyl silicone oil was replaced with one having a low refractive index (SH510 manufactured by Toray Dow Corning, viscosity 100 mm 2 / s at 25 ° C., refractive index 1.425). evaluated. The results are shown in Tables 1 and 2.
［比較例７］
ステアリン酸亜鉛の被覆量を１３．０ｇから１．０ｇに変更した以外は、実施例３と同様の操作を行い予備発泡した結果、篩上に残った発泡時結合量は１０．１％と非常に多くなり、篩を通過したものにも、双子や三つ子状に結合した粒子が多数認められる為、成形評価は取りやめた。
[Comparative Example 7]
Except that the coating amount of zinc stearate was changed from 13.0 g to 1.0 g, pre-foaming was carried out in the same manner as in Example 3. As a result, the binding amount remaining on the sieve was 10.1%, which was extremely low. Since many particles bound in twins and triplets were observed even after passing through the sieve, the molding evaluation was canceled.
［比較例８］
ステアリン酸亜鉛の被覆量を１３．０ｇから３５．０ｇに変更した以外は、実施例１と同様の操作を行い同様に評価した。結果を表１，２に示す。
[Comparative Example 8]
The same operation as in Example 1 was performed, except that the coating amount of zinc stearate was changed from 13.0 g to 35.0 g. The results are shown in Tables 1 and 2.
［比較例９］
気泡調整剤の添加量を０．５１ｇから１．０１ｇに変更した以外は、実施例６と同様の操作を行い粒子径約１．０ｍｍの発泡性スチレン樹脂粒子を得た。この発泡性スチレン樹脂粒子を嵩発泡倍数６０倍に発泡した発泡粒子表層部の平均気泡径は３５μｍであった。
この発泡性スチレン樹脂粒子について、実施例１と同様の操作を行い同様に評価した。結果を表１，２に示す。
[Comparative Example 9]
Except having changed the addition amount of the bubble regulator from 0.51 g to 1.01 g, the same operation as Example 6 was performed and the expandable styrene resin particle of about 1.0 mm particle diameter was obtained. The average cell diameter of the surface layer of the expanded particles obtained by expanding the expandable styrene resin particles to a bulk expansion ratio of 60 times was 35 μm.
About this expandable styrene resin particle, operation similar to Example 1 was performed and evaluated similarly. The results are shown in Tables 1 and 2.
［比較例１０］
撹拌機を備えた内容積５２リットルの反応器に、蒸留水１８ｋｇ、ピロリン酸マグネシウム６５ｇ、ドデシルベンゼンスルホン酸ナトリウム２．５ｇを入れ、実施例１で用いたスチレン樹脂種粒子５．０ｋｇを加えて撹拌し懸濁させた。
次いで予め用意した蒸留水１５００ｇ、ピロリン酸マグネシウム５．０ｇ、ドデシルベンゼンスルホン酸ナトリウム１．０ｇの分散液に、重合開始剤としてベンゾイルパーオキサイド７６．１ｇ及びｔ−ブチルパーオキシベンゾエート１６．９ｇをスチレン２１６０ｇに溶解して添加し、ホモミキサーにかけて調製した懸濁液を７６℃に保持した反応器に加えた。
撹拌しながら７６℃で１時間保持し、スチレン樹脂種粒子に重合開始剤と気泡調整剤を吸収させた後、反応器内にスチレンを５９００ｇ／ｈｒの速度で連続的に２．５時間供給するとともに、スチレン供給終了時に懸濁液が１０６℃となるように反応器を連続的に昇温した。引き続き１２０℃まで昇温して３０分保持した後、蒸留水２０００ｇにピロリン酸マグネシウム６．５ｇ、ドデシルベゼンスルホン酸ナトリウム０．６ｇを加えた分散液に、発泡助剤としてシクロヘキサン１７５．３ｇ、ジイソブチルアジペート（ＤＩＢＡ）１５３．４ｇを加えてホモミキサーにかけた懸濁液を反応器内に圧入した。その後、１００℃まで冷却して工業用ブタン（イソブタン／ノルマルブタン＝３５／６５）１９７５ｇを圧入して１００℃で３時間保持した後、２０℃まで冷却して取り出し、洗浄、脱水、乾燥した。さらに発泡後の気泡径が完全に安定するまで１８℃で５日間熟成させて、粒子径約１．０ｍｍの発泡性スチレン樹脂粒子を得た。この発泡性スチレン樹脂粒子を嵩発泡倍数６０倍に発泡した発泡粒子表層部の平均気泡径は１８２μｍであった。
この発泡性スチレン樹脂粒子について、実施例１と同様の操作を行い同様に評価した。結果を表１，２に示す。
[Comparative Example 10]
Into a reactor having an internal volume of 52 liters equipped with a stirrer, 18 kg of distilled water, 65 g of magnesium pyrophosphate and 2.5 g of sodium dodecylbenzenesulfonate were added, and 5.0 kg of the styrene resin seed particles used in Example 1 were added. Stir and suspend.
Next, 76.1 g of benzoyl peroxide and 16.9 g of t-butylperoxybenzoate were used as a polymerization initiator in a dispersion of 1500 g of distilled water prepared in advance, 5.0 g of magnesium pyrophosphate and 1.0 g of sodium dodecylbenzenesulfonate. It was dissolved in 2160 g and added, and the suspension prepared by applying a homomixer was added to the reactor maintained at 76 ° C.
The mixture is held at 76 ° C. for 1 hour with stirring to absorb the polymerization initiator and the bubble regulator in the styrene resin seed particles, and then styrene is continuously fed into the reactor at a rate of 5900 g / hr for 2.5 hours. At the same time, the temperature of the reactor was continuously raised so that the suspension became 106 ° C. at the end of the styrene supply. Subsequently, the temperature was raised to 120 ° C. and held for 30 minutes, and then 175.3 g of cyclohexane as a foaming aid was added to a dispersion obtained by adding 6.5 g of magnesium pyrophosphate and 0.6 g of sodium dodecylbezenesulfonate to 2000 g of distilled water. A suspension obtained by adding 153.4 g of diisobutyl adipate (DIBA) and applying it to a homomixer was pressed into the reactor. Then, after cooling to 100 ° C., 1975 g of industrial butane (isobutane / normal butane = 35/65) was injected and held at 100 ° C. for 3 hours, then cooled to 20 ° C., taken out, washed, dehydrated and dried. Further, the foamed styrene resin particles having a particle diameter of about 1.0 mm were obtained by aging at 18 ° C. for 5 days until the bubble diameter after foaming was completely stabilized. The average cell diameter of the surface layer of the expanded particles obtained by expanding the expandable styrene resin particles to a bulk expansion ratio of 60 times was 182 μm.
About this expandable styrene resin particle, operation similar to Example 1 was performed and evaluated similarly. The results are shown in Tables 1 and 2.
［比較例１１］
発泡助剤（シクロヘキサン１７５．３ｇ、ＤＩＢＡ１５３．４ｇ）の他に、ジメチルシリコーンオイル（信越化学工業株式会社製ＫＦ−９６−１００ｃｓ、２５℃における比重０．９６５）２１．１ｇ加えてホモミキサーにかけた懸濁液を反応器に圧入し、工業用ブタン圧入後１００℃で１２時間保持した以外は、実施例１と同様の操作を行い粒子径約１．０ｍｍのジメチルシリコーンオイルが粒子表層付近に含浸された発泡性スチレン樹脂粒子を得た。この発泡性スチレン樹脂粒子を嵩発泡倍数６０倍に発泡した発泡粒子表層部の平均気泡径は６８μｍであった。
この発泡性スチレン樹脂粒子１０ｋｇに対して、比較例６で用いたメチルフェニルシリコーンオイル（ＳＨ５１０）５．０ｇを内容積約３０リットルのタンブラーミキサーを用いて、毎分３０回転で約５分間混合して樹脂粒子の表面に被覆した後、ベヘン酸トリグリセライド１４．０ｇ、エチレンビスステアリン酸アミド６．０ｇを添加して更に１５分間混合して、樹脂粒子の表面に被覆した。
得られた発泡性スチレン樹脂粒子について、実施例１と同様の評価を行った。この発泡性スチレン樹脂粒子から得られた成形品は、光沢度が低く、水漏れ試験において容器底部の全面から水漏れが認められた。結果を表１，２に示す。
[Comparative Example 11]
In addition to the foaming aid (cyclohexane 175.3 g, DIBA 153.4 g), 21.1 g of dimethyl silicone oil (KF-96-100cs manufactured by Shin-Etsu Chemical Co., Ltd., specific gravity 0.965 at 25 ° C.) was added and subjected to a homomixer. The suspension was press-fitted into the reactor and the same operation as in Example 1 was carried out except that the butane was press-fit for industrial use and maintained at 100 ° C. for 12 hours, and dimethyl silicone oil having a particle size of about 1.0 mm was impregnated near the particle surface layer. Thus obtained expandable styrene resin particles were obtained. The average cell diameter of the surface layer of the expanded particles obtained by expanding the expandable styrene resin particles to a bulk expansion ratio of 60 times was 68 μm.
To 10 kg of the expandable styrene resin particles, 5.0 g of methylphenyl silicone oil (SH510) used in Comparative Example 6 was mixed for about 5 minutes at 30 rpm with a tumbler mixer having an internal volume of about 30 liters. After coating the surface of the resin particles, 14.0 g of behenic acid triglyceride and 6.0 g of ethylenebisstearic acid amide were added and mixed for another 15 minutes to coat the surface of the resin particles.
The obtained expandable styrene resin particles were evaluated in the same manner as in Example 1. The molded product obtained from the expandable styrene resin particles had low gloss, and water leakage was observed from the entire bottom surface of the container in the water leakage test. The results are shown in Tables 1 and 2.
［比較例１２］
実施例１で得られた発泡性スチレン樹脂粒子１０ｋｇに対して、メチルフェニルシリコーンオイル（信越化学工業株式会社製ＫＦ−５４、２５℃における粘度４００ｍｍ２／ｓ、屈折率１．５０５）５．０ｇ、ステアリン酸亜鉛１０．０ｇ、硬化牛脂油６０．０ｇ（日本油脂株式会社製、牛脂極度硬化油、融点約５９℃、主成分はステアリン酸トリグリセライド及びパルミチン酸トリグリセライド混合物）を内容積約３０リットルのタンブラーミキサーを用いて、毎分３０回転で約１５分間混合して、樹脂粒子の表面に被覆した。
得られた発泡性スチレン樹脂粒子について、実施例１と同様の評価を行った。この発泡性スチレン樹脂粒子からは短い冷却時間で成形品を得ることができるが、得られた成形品は強度が著しく劣り、光沢度の低いものであった。結果を表１，２に示す。
[Comparative Example 12]
5.0 g of methylphenylsilicone oil (KF-54 manufactured by Shin-Etsu Chemical Co., Ltd., viscosity 400 mm 2 / s at 25 ° C., refractive index 1.505) with respect to 10 kg of expandable styrene resin particles obtained in Example 1. , Zinc stearate 10.0 g, hydrogenated beef tallow oil 60.0 g (manufactured by Nippon Oil & Fats Co., Ltd., beef tallow extremely hardened oil, melting point about 59 ° C., main component is a mixture of stearic acid triglyceride and palmitic acid triglyceride) with an internal volume of about 30 liters Using a tumbler mixer, mixing was performed at 30 rpm for about 15 minutes to coat the surface of the resin particles.
The obtained expandable styrene resin particles were evaluated in the same manner as in Example 1. A molded product can be obtained from the expandable styrene resin particles in a short cooling time. However, the obtained molded product was remarkably inferior in strength and low in gloss. The results are shown in Tables 1 and 2.
表１，２の結果から、本発明に係る実施例１〜７で製造した発泡性スチレン樹脂粒子は、予備発泡−型内発泡成形する際に、従来の型内発泡成形で使用するより低圧の蒸気でも発泡粒子同士を十分融着させることができ、低圧の蒸気で成形を行うことにより、成形時の冷却時間が短くなり、短い成形サイクルで、十分な強度を持ち、表面光沢に優れた発泡成形品が得られることがわかる。
From the results of Tables 1 and 2, the expandable styrene resin particles produced in Examples 1 to 7 according to the present invention had a lower pressure than that used in the conventional in-mold foam molding when pre-foaming-in-mold foam molding was performed. Vaporized particles can be sufficiently fused with steam, and by molding with low-pressure steam, the cooling time during molding is shortened, foaming with sufficient strength and excellent surface gloss is achieved with a short molding cycle. It turns out that a molded article is obtained.
Claims (7)
を用いて嵩発泡倍数６０倍に換算した発泡粒子表層部の平均気泡径Ｄが、４０μｍ≦Ｄ≦１５０μｍの関係を満たすことを特徴とする請求項１〜３のいずれかに記載の発泡性スチレン系樹脂粒子。 The average cell diameter D ′ of the surface portion of the expanded particle when expanded to a bulk expansion ratio X times is expressed by the following formula (1).
The foamable styrene according to any one of claims 1 to 3, wherein the average cell diameter D of the surface layer portion of the expanded particle converted to a bulk expansion ratio 60 times using the above satisfies a relationship of 40 µm ≤ D ≤ 150 µm. Resin particles.
The method for producing a styrene-based resin foam molded article according to claim 6, wherein the expansion ratio is in the range of 20 to 90 times.
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| JP2011153261A (en) * | 2010-01-28 | 2011-08-11 | Sekisui Plastics Co Ltd | Foamable polystyrene-based resin particles, polystyrene-based resin prefoamed particles, polystyrene-based resin foam molding, and method of producing the same |
| JP2014070150A (en) * | 2012-09-28 | 2014-04-21 | Sekisui Plastics Co Ltd | Polystyrene-based foamed molding, production method thereof, and foamed resin-made container |
| JP2018058957A (en) * | 2016-10-03 | 2018-04-12 | 株式会社カネカ | Foamable polystyrene resin particle |
| JP2018119109A (en) * | 2017-01-27 | 2018-08-02 | 株式会社カネカ | Foamable polystyrene resin particle |
| JP2019031587A (en) * | 2017-08-04 | 2019-02-28 | 株式会社カネカ | Foamable polystyrene resin particle |
| JP2019065074A (en) * | 2017-09-28 | 2019-04-25 | 株式会社カネカ | Expandable polystyrene resin particle, polystyrene pre-expanded particle, and foam molding |
| JP2020152843A (en) * | 2019-03-20 | 2020-09-24 | 株式会社カネカ | Foamable polystyrene resin particle, polystyrene preliminary foam particle, and foam molding |
| JP2021134302A (en) * | 2020-02-28 | 2021-09-13 | 積水化成品工業株式会社 | Styrenic resin foam-molded material, expandable styrenic resin particle, pre-expanded styrenic resin particle and production method for expandable styrenic resin particle |
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Cited By (13)
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| JP2011153261A (en) * | 2010-01-28 | 2011-08-11 | Sekisui Plastics Co Ltd | Foamable polystyrene-based resin particles, polystyrene-based resin prefoamed particles, polystyrene-based resin foam molding, and method of producing the same |
| JP2014070150A (en) * | 2012-09-28 | 2014-04-21 | Sekisui Plastics Co Ltd | Polystyrene-based foamed molding, production method thereof, and foamed resin-made container |
| JP2018058957A (en) * | 2016-10-03 | 2018-04-12 | 株式会社カネカ | Foamable polystyrene resin particle |
| JP2018119109A (en) * | 2017-01-27 | 2018-08-02 | 株式会社カネカ | Foamable polystyrene resin particle |
| JP7049767B2 (en) | 2017-01-27 | 2022-04-07 | 株式会社カネカ | Effervescent polystyrene resin particles |
| JP7009109B2 (en) | 2017-08-04 | 2022-01-25 | 株式会社カネカ | Effervescent polystyrene resin particles |
| JP2019031587A (en) * | 2017-08-04 | 2019-02-28 | 株式会社カネカ | Foamable polystyrene resin particle |
| JP6999343B2 (en) | 2017-09-28 | 2022-01-18 | 株式会社カネカ | Effervescent polystyrene resin particles, polystyrene pre-expanded particles and foam molded products |
| JP2019065074A (en) * | 2017-09-28 | 2019-04-25 | 株式会社カネカ | Expandable polystyrene resin particle, polystyrene pre-expanded particle, and foam molding |
| JP2020152843A (en) * | 2019-03-20 | 2020-09-24 | 株式会社カネカ | Foamable polystyrene resin particle, polystyrene preliminary foam particle, and foam molding |
| JP2021134302A (en) * | 2020-02-28 | 2021-09-13 | 積水化成品工業株式会社 | Styrenic resin foam-molded material, expandable styrenic resin particle, pre-expanded styrenic resin particle and production method for expandable styrenic resin particle |
| JP7425628B2 (en) | 2020-02-28 | 2024-01-31 | 積水化成品工業株式会社 | Method for producing styrenic resin foam molded articles, expandable styrenic resin particles, pre-expanded styrenic resin particles, and expandable styrenic resin particles |
| WO2022030230A1 (en) * | 2020-08-07 | 2022-02-10 | 株式会社カネカ | Foamable polystyrene resin particles, polystyrene pre-foamed particles, and foamed molded product |
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