1325435 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種發泡性聚苯乙烯系樹脂粒子及其製造 方法、使用該發泡性聚苯乙烯系樹脂粒子而製造之預發泡 粒子及發泡成形品、以及於由該發泡成形品所構成的容器 中包裝有食品之食品包裝體。 【先前技術】 先前，使苯乙烯系樹脂粒子中浸滲發泡劑而形成發泡性 聚苯乙烯系樹脂粒子，再將該樹脂粒子進行預發泡而製造 預發泡粒子，將該預發泡粒子填充於成形機之成形模内， 隨後加熱使其發泡而相互熔合一體化，從而製造具有所期 • 望形狀之發泡成形容器。 .如上所述，發泡成形容器，係藉由預發泡粒子自身之發 泡壓力，而使得預發泡粒子發泡所形成的發泡粒子之間熱 熔合一體化而成者；但於該等發泡粒子之間的接觸部分， φ 發泡粒子之間並不完全地熱熔合，而僅部分地熱熔合一體 化0 因此，發泡成形容器，例如即使發泡粒子之間處於良好 狀I即於發Z包成形谷器之剖面中發泡粒子表面之間處於 目視下完全熱熔合-體化之狀態，但發泡粒子之間的接觸 部分中之起因於非熱熔合部分之間隙沿内外方向連續，因 而形成於目視下無法確認之微細毛細管在發泡成形容器内 外面之間貫通之狀態。 該情形可根據以下現象之產生^確認：若於發泡成形 H4931.doc 1325435 容器内加入含有界面活性劑的染料水，再持續放置特定時 間’則發泡成形容器内的染料水會通過於發泡粒子間所形 成之毛細管向外部滲出。[Technical Field] The present invention relates to an expandable polystyrene resin particle, a method for producing the same, and a pre-expanded particle produced by using the expandable polystyrene resin particle And a foamed molded article and a food package in which a food is packaged in a container composed of the foamed molded article. [Prior Art] The styrene resin particles are impregnated with a foaming agent to form foamable polystyrene resin particles, and the resin particles are pre-expanded to produce pre-expanded particles. The foam particles are filled in a forming mold of a molding machine, and then heated to be foamed to be fused and integrated with each other, thereby producing a foam molded container having a desired shape. As described above, the foamed molded container is obtained by thermally fusing the expanded particles formed by foaming the pre-expanded particles by the foaming pressure of the pre-expanded particles themselves; The contact portion between the expanded particles, the φ foamed particles are not completely thermally fused, but only partially thermally fused and integrated. Therefore, the foamed molded container, for example, even if the expanded particles are in a good shape I The surface of the foamed particles in the cross section of the Z-shaped shaped barn is in a state of being completely thermally fused-formed under visual observation, but the gap between the expanded particles due to the non-thermal fusion portion is continuous in the inner and outer directions. Therefore, a microcapillary which cannot be confirmed by visual observation is formed in a state of being penetrated between the inside and the outside of the foamed molded container. In this case, it can be confirmed that if the dye water containing the surfactant is added to the foam forming H4931.doc 1325435 container and then kept for a certain period of time, the dye water in the foamed shaped container will pass through. The capillary formed between the bubble particles oozes to the outside.
另外，於使用如此發泡成形容器作為如咖啡之飲料用杯 之情形時，雖在實用上並不產生任何障礙，但存在以下問 題：若於發泡成形容器内長期持續保存油性食品類，例如 炸甜圈、漢堡包、油炸雞、人造奶油等沙拉油、含有油脂 等之食品，則該等油性食品類中所含有的油分會通過於發 泡成形谷器中形成之毛細管向外部滲出。 同樣，於發泡成形容器内，若同時容納方便麵及含有咖 喱粉的輔料類而加以保存，則咖喱粉的黃色色素會通過發 泡成形容器的毛細管向發泡成形容器外面滲出，故存在商 品價值受損之問題。Further, when such a foamed molded container is used as a cup for a coffee beverage, there is no problem in practical use, but there is a problem that if the oily food is continuously stored in the foamed molded container for a long period of time, for example, A salad oil such as a doughnut, a hamburger, a fried chicken, or a margarine, or a food containing oil or the like, the oil component contained in the oily food may be exuded to the outside by a capillary formed in the foam forming vessel. Similarly, when the instant noodles and the curcum powder-containing excipients are simultaneously stored in the foam-molded container, the yellow pigment of the curry powder oozes out through the capillary of the foam-molded container to the outside of the foam-molded container, so that there is a commercial value. Damaged problem.
因此’於專利文獻！中，提出有_發泡性聚苯乙缔系樹 脂粒子，其特徵在於：預先以表面層包覆發泡性聚苯乙烯 系樹脂粒子之表面；相對於1GGf量份之發泡性聚苯乙稀 系樹脂粒子，該表皮層中包含G.3〜Q.6f量份之硬脂酸辞、 及(M〜0.4質量份之聚乙二醇水溶液，該聚乙二醇水溶液含 有20〜50質量％之質量平均分子量為咖〜繼之聚乙二醇。 將上述發祕聚苯乙料樹絲子進行發泡成形 而獲传之發泡成形品’雖可見某種程度之防止油分渗出之 效果，但因成形體對油分之耐性 對於防止油分滲出而言並不充分不足故於長期保管期間 於聚苯乙烯系樹脂粒子中’為賦予某種程度之耐油性， 114931.doc 1^25435 可列舉使聚苯乙烯系樹脂具有交聯結構之方法。防止油分 自成形品中滲出雖並非直接目的，但業者一直以來進行有 使聚苯乙烯系樹脂粒子具有交聯結構之嘗試。 於專利文獻2中，提出有—發純聚笨乙烯系樹脂粒子 之製造方法，其係以製造可與聚苯乙稀系樹脂混合成形之 :泡性聚苯乙稀系樹脂為㈣；其中，於懸濁有發泡性聚 苯乙烯粒子之水性介質+，緩慢添加由mo質量％二 稀基苯及99.95〜99.G質量％苯乙稀單體所組成之聚合性 單體混合物，使得上述發泡性聚苯乙烯系樹脂粒子達 90 50質里％、上述聚合性單體混合物達1〇〜質量％，且 於聚合催化劑存在下進行聚合，藉此於發泡性聚苯乙稀表 面上形成苯乙烯-二乙烯基苯共聚物。 該方法雖可使表層部分具有交聯結構但在預先藉由發 ，使聚苯乙稀系樹脂膨潤從而使含有交聯性單體的苯乙 ，单體包含於其中時，苯乙烯單體浸透至粒子較為中心 Z ’雖較粒子表層的交聯度低，但粒子内部亦形成交聯結 構。 若料為杯㈣包裝容㈣通常使用之粒徑小之樹脂粒 子路則父聯會更顯著地向粒子内部進行。為維持如此粒子 之發泡能力，若金^ w 士、& A p + …、了成為未反應部分的苯乙烯單體等的容 劑之成分’則並不具有良好發泡能力。然而，含有大量'容 劑成分者，並不適宜作為包裝食品之容器。有大“ ;專利文獻3中’為提昇杯成形品之強度，提出 一以苯乙婦-二乙稀基苯共聚物進行改性之笨乙烯系聚合 114931.doc 物珠粒。然而，於該方法， 中雖成形品之強度得以提昇，但 因粒子整體比較均勻地經 田又聯結構而被改性，故發泡能 力欠缺，因而為獲得且良 设寻/、良好外觀之成形品必須進行額外之 加熱，有損生產性。 :專利文獻4中’揭不有一發泡性苯乙烯系聚合物 粒子之製k方法(種子聚合法)，其係藉由於含苯乙烯系聚 合物粒種的水性懸濁液中，連續或間斷地添加苯乙稀系單 體及聚合引發劑，而使得該苯乙㈣單體與該苯乙稀系聚 合物粒種聚合，以獲得苯乙烯系聚合物粒子，再使該苯乙 稀系聚σ物粒子中浸渗易揮發性發泡劑之發泡性聚苯乙婦 系聚合物粒子之製造方法；纟中，在將上述苯乙烯系聚合 物粒種的量與用以獲得目的笨乙烯系聚合物粒子所必需的 本乙烯系單體的量之合計量設為1GG質量份時，自該苯乙 烯系聚合物粒種的量與已添加的苯乙烯系單體之合計量達 質量伤時起直直至結束添加該苯乙烯系單體且結束聚合 反應之期間，相對於該合計量1〇〇質量份，添加〇 〇〇5〜〇 〇2 質量份之交聯性單體。 …而，依照上述製造方法製造之發泡性聚苯乙烯系聚合 物粒子，可有效地堵塞使用該發泡性聚苯乙烯系聚合物粒 子而獲得之發泡成形品之預發泡粒子之間的間隙，但對於 如上述之油分或黃色色素通過在發泡成形容器中所形成的 毛細管滲出至外部之問題，因對油分的耐性不足故無法充 分解決之。 [專利文獻1]日本專利特開2005-8797號公報 114931.doc 1325435 [專利文獻2]日本專利特公昭48 44656號公報 [專利文獻3]曰本專利特開昭62_181344號公報 [專利文獻4]日本專利特開平9_221563號公報 [發明所欲解決之問題] 本發明者們經過努力研究，結果發現：於發泡成形容器 中油分或黃色色素產生滲出之處，發泡粒子的熱熔合部分 起伏而形成皺紋，由於油分或黃色色素而造成發泡成形容 器變質；另一方面，於未產生油分或黃色色素滲出之處， 於發泡粒子的熱熔合部分並未產生起伏現象，係未變形之 狀態’並未因油分或黃色色素而造成變質。進而，為防止 於發/包成形容器中油分或黃色色素渗出，必須提昇發泡成 形品之耐油性，尤其是提昇發泡成形品的發泡粒子之間的 熱^§合部分之耐油性。 本發明之目的係提供發泡性聚苯乙烯系樹脂粒子及其製 造方法、以及使用該發泡性聚苯乙烯系樹脂粒子而製造之 φ 發泡成形品及於由該發泡成形品所構成的容器中包裝有食 品之食品包裝體；其中，使用該發泡性聚苯乙烯系樹脂粒 子’可獲得即使於在内部長期持續保存食品等中所含有的 油分及咖喱粉等色素、或者在内部以特定時間持續容納含 有界面活性劑等液體之情形時，亦不會向外部渗出之發泡 成形品，且發泡性優異。 【發明内容】 為達成上述目的，本發明提供一種發泡性苯乙婦系樹脂 粒子’其特徵在於，其係於聚苯乙稀系樹脂粒子表面#有 114931.doc • 10· 1325435 使父聯性單體與$乙稀系單體聚合而形纟的表I、並於其 中浸滲易揮發性發泡劑而成之發泡成形用發泡性聚苯乙烯 系樹脂粒子； 使該樹脂粒子於四氫呋喃中飽和膨潤時之表層厚度為 3〜100 μπι之範圍，且相對於該樹脂粒子的總量，不溶於四 氫呋喃之.凝膠成分為10〜50質量。/〇之範圍。 於本發明之發泡性苯乙烯系樹脂粒子中’上述表層厚度 之測定，較好的是藉由以下步驟而實施：將樹脂粒子浸 潰於四氫咬喃中飽和膨潤化；（2)繼而，將飽和膨潤化之樹 脂粒子自四氫呋喃中分離；（3)繼而，將分離後之樹脂粒子 浸潰於曱基丙烯酸甲酯中，以曱基丙烯酸甲酯置換經飽和 膨潤化樹脂粒子内部之四氫呋喃；（4)繼而，使甲基丙稀酸 甲醋聚合成聚甲基丙烯酸曱酯固化體，將樹脂粒子以膨潤 狀態固定於該聚甲基丙烯酸甲酯固化體中；繼而，沿通 過樹脂粒子中心之面切斷上述聚甲基丙烯酸甲酯固化體； (6)繼而，觀察該剖面，測量樹脂粒子之表層厚度。 又’本發明提供一種發泡性苯乙稀系樹脂粒子之製造方 法，其特徵在於’使100質量份含苯乙烯系樹脂之粒種分 散於水性介質中，隨後於該分散液中添加1 5~1 00質量份之 苯乙烯系單體以及0.03〜1.0質量份之交聯性單體，使其被 上述粒種吸收聚合而得苯乙婦系樹脂粒子，然後使易揮 發性發泡劑浸滲以製造發泡性苯乙烯系樹脂粒子之方法； 將聚合過程中於成長粒子117的苯乙烯系樹脂比例設為 80〜100質量％之範圍，而獲得上述本發明之發泡性笨乙稀 114931.doc 1325435 系樹脂粒子。 又，本發明提供一種預發泡粒子，其係使上述本發明之 發泡性聚苯乙烯系樹脂粒子預發泡而獲得。 又’本發明提供一種發泡成形品’其特徵在於，其係使 上述本發明之預發泡粒子發泡成形而獲得。 又’本發明提供一種食品包裝體，其特徵在於，於包含 上述本發明之發泡成形品的容器内，包裝有油性食品或含 食用油脂與色素之食品。 [發明之效果] 使本發明之發泡性聚笨乙烯系樹脂粒子預發泡而獲得預 發泡粒子，再將該預發泡粒子發泡成形而獲得發泡成形 品，即使於該發泡成形品内部長期持續容納含油分的食品 或者含有界面活性劑的液體之情形時，發泡性粒子之間的 熱熔合界面亦不會被油分、色素或界面活性劑等所侵入。 因此，可防止含油分、色素、界面活性劑的液體等通過發 • 泡粒子之間的熱熔合界面而滲出至發泡成形品外面之問 題。 進而，因纟發明之發泡成形品之外觀優#、表面之發泡 粒子間之空隙少’故其表面印刷性優異。 【實施方式】 本發明之發泡性苯乙稀系樹脂粒子，其係於聚苯乙稀系 樹脂粒子表面設置有使交聯性單體與苯乙稀系單體聚合而 形成之表層，再使其等中浸滲易揮發性發泡劑而成；其特 徵在於，將該樹脂粒子於25t:、常壓下於四氫呋喃（以下 114931.doc -12· 1325435 稱為THF)中進行飽和膨潤時之表層厚度為3〜刚㈣範圍， 且相對於該樹脂粒子總量，不溶於THF之凝膠成分為 10〜50質量％之範圍。 構成本發明之發泡性聚苯乙歸系樹脂粒子的表層以外部 分之聚苯乙烯系樹脂，並無特別限定，例如可例舉：苯乙 烯、CX-甲基苯乙稀、乙稀基甲苯、氣苯乙稀、乙基苯乙 稀、異丙基苯乙稀、二甲基笨乙稀等苯乙稀系單體之均聚So in the patent literature! In the case of the foamed polystyrene-based resin particles, the surface of the foamable polystyrene resin particles is coated with a surface layer in advance; and the foamable polyphenylene is added in an amount of 1 GGf. a rare resin particle containing G.3~Q.6f parts of stearic acid and (M~0.4 parts by mass of a polyethylene glycol aqueous solution containing 20 to 50 masses) The mass average molecular weight of % is PEG = followed by polyethylene glycol. The foamed molded article obtained by foaming and molding the above-mentioned vesicular polystyrene tree filaments can be seen to some extent to prevent oil oozing. The effect is that the resistance of the molded body to the oil is not sufficiently insufficient to prevent the oil from oozing out, so that in the long-term storage period, the polystyrene resin particles are provided with a certain degree of oil resistance, 114931.doc 1^25435 In order to prevent the oil component from oozing out of the molded article, it is not a direct object, but attempts have been made to make the polystyrene resin particles have a crosslinked structure. Patent Document 2 In the case of A method for producing pure polystyrene-based resin particles, which is produced by mixing with a polystyrene-based resin: a foaming polystyrene resin is (4); wherein, foaming polyphenylene is suspended in suspension An aqueous medium of ethylene particles +, a polymerizable monomer mixture composed of mo% by mass of diphenylbenzene and 99.95 to 99.g mass% of styrene monomer is slowly added to make the above-mentioned expandable polystyrene resin particles Up to 90% by mass, the above polymerizable monomer mixture is 1% by mass to mass%, and polymerization is carried out in the presence of a polymerization catalyst, whereby styrene-divinylbenzene copolymerization is formed on the surface of the foamable polystyrene Although the surface portion of the surface layer has a crosslinked structure, the polystyrene resin is swollen in advance to cause the phenylethyl group containing the crosslinkable monomer, and the monomer is contained therein, the styrene single The body is saturated to the center of the particle. Although the cross-linking degree of the particle surface layer is lower than that of the surface layer of the particle, the cross-linked structure is also formed inside the particle. If the material is a cup (four) package capacity (4), the resin particle path with a small particle size is usually used. Significantly proceed inside the particle. In order to maintain the foaming ability of such particles, if the components of the resin such as styrene monomer which is an unreacted portion, such as gold, and the like, do not have good foaming ability. It is not suitable as a container for packaged foods. It has a large size. In Patent Document 3, in order to enhance the strength of the molded cup, a styrene-diethyl benzene copolymer is proposed. Stupid vinyl polymerized 114931.doc beads. However, in this method, although the strength of the molded article is improved, the foaming ability is lacking because the particles are uniformly modified by the field and the structure. Therefore, in order to obtain and obtain a good appearance, a molded article of good appearance must be subjected to additional heating, which impairs productivity. Patent Document 4 discloses a method for producing a foaming styrene polymer particle (seed) a polymerization method in which a styrene monomer and a benzene are continuously or intermittently added in an aqueous suspension containing a styrene-based polymer particle to cause the phenethyl (tetra) monomer and the benzene Ethylene polymer particles are polymerized to a method for producing styrene polymer particles and foaming polystyrene polymer particles impregnated with the volatility foaming agent in the styrene-based poly-σ particles; When the total amount of the styrene-based polymer particles and the amount of the vinyl-based monomer necessary for obtaining the objective ethylene-based polymer particles is 1 GG by mass, the styrene-based polymer particles are used. When the amount of the styrene-based monomer to be added is up to the mass of the styling monomer, the styrene-based monomer is added until the polymerization reaction is completed, and 〇〇〇 is added in an amount of 1 part by mass based on the total amount. 5 to 〇〇 2 parts by mass of a crosslinkable monomer. In addition, the expandable polystyrene polymer particles produced by the above-described production method can effectively block between the pre-expanded particles of the foamed molded article obtained by using the expandable polystyrene polymer particles. In the gap, the problem that the oil or yellow pigment as described above leaks to the outside through the capillary formed in the foamed molded container cannot be sufficiently solved because the resistance to oil is insufficient. [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Application Laid-Open No. Hei 9-221563 (Problem to be Solved by the Invention) As a result of intensive studies, the present inventors have found that in the case where the oil or yellow pigment is oozing out in the foamed molded container, the heat-fused portion of the expanded particles is undulated. Wrinkles are formed, and the foamed molded container is deteriorated due to oil or yellow pigment; on the other hand, in the place where no oil or yellow pigment is oozing out, no undulation occurs in the heat-fused portion of the expanded particles, and the state is not deformed. 'No deterioration due to oil or yellow pigment. Further, in order to prevent the oil component or the yellow pigment from oozing out in the hair/pack forming container, it is necessary to improve the oil resistance of the foamed molded article, in particular, to improve the oil resistance of the heat-bonding portion between the expanded particles of the foamed molded article. . An object of the present invention is to provide expandable polystyrene resin particles, a method for producing the same, and a φ foam molded article produced by using the expandable polystyrene resin particles and comprising the foam molded article. In the container, the food package of the food is packaged, and the foamable polystyrene resin particles are used to obtain a coloring matter such as oil and curry powder contained in the food or the like for a long period of time, or internally. When the liquid containing a surfactant or the like is continuously stored for a specific period of time, the foamed molded article does not ooze out to the outside, and the foaming property is excellent. SUMMARY OF THE INVENTION In order to achieve the above object, the present invention provides a foamable styrene-based resin particle which is characterized in that it is attached to the surface of a polystyrene resin particle #114931.doc • 10· 1325435 a foamable polystyrene resin particle for foam molding in which a monomer and a vinyl monomer are polymerized and formed into a form, and a volatile foaming agent is impregnated therein; The thickness of the surface layer when saturated and swelled in tetrahydrofuran is in the range of 3 to 100 μm, and is insoluble in tetrahydrofuran with respect to the total amount of the resin particles. The gel component is 10 to 50 mass. / Range of 〇. In the foamable styrene resin particles of the present invention, the measurement of the thickness of the surface layer is preferably carried out by subjecting the resin particles to saturation swelling in a tetrahydrogenate; (2) Separating the saturated and swelled resin particles from tetrahydrofuran; (3) subsequently, the separated resin particles are impregnated into methyl methacrylate, and the tetrahydrofuran inside the saturated swelled resin particles is replaced with methyl methacrylate (4) Then, the methyl methacrylate methyl vinegar is polymerized into a polymethyl methacrylate cured body, and the resin particles are fixed in the swelled state in the polymethyl methacrylate cured body; The above-mentioned polymethyl methacrylate solidified body was cut off from the center; (6) Then, the cross section was observed, and the surface layer thickness of the resin particles was measured. Further, the present invention provides a method for producing foamable styrene-based resin particles, characterized in that '100 parts by mass of a styrene-based resin-containing particle is dispersed in an aqueous medium, and then 15 5 is added to the dispersion ～100 parts by mass of a styrene monomer and 0.03 to 1.0 part by mass of a crosslinkable monomer, which are absorbed and polymerized by the above-mentioned seed particles to obtain styrene-based resin particles, and then immersed in a volatile foaming agent A method of producing foamable styrene-based resin particles; and the ratio of the styrene-based resin to the grown particles 117 in the polymerization process is in the range of 80 to 100% by mass to obtain the above-described foaming stupid ethylene of the present invention. 114931.doc 1325435 is a resin particle. Moreover, the present invention provides a pre-expanded particle obtained by pre-expanding the expandable polystyrene-based resin particles of the present invention. Further, the present invention provides a foamed molded article obtained by foam molding the pre-expanded particles of the present invention. Further, the present invention provides a food package comprising an oily food or a food containing edible fats and oils and a coloring matter in a container comprising the foamed molded article of the present invention. [Effect of the Invention] The foamable polystyrene-based resin particles of the present invention are pre-expanded to obtain pre-expanded particles, and the pre-expanded particles are foam-molded to obtain a foamed molded article, even in the foaming. When the inside of the molded article continuously holds the oil-containing food or the surfactant-containing liquid for a long period of time, the heat fusion interface between the foamable particles is not invaded by oil, color, surfactant, or the like. Therefore, it is possible to prevent the oil containing oil, the pigment, the surfactant, and the like from oozing out to the outside of the foamed molded article through the heat fusion interface between the foam particles. Further, since the appearance of the foamed molded article of the invention is excellent, and the gap between the foamed particles on the surface is small, the surface printability is excellent. [Embodiment] The foamable styrene-based resin particles of the present invention are provided with a surface layer formed by polymerizing a crosslinkable monomer and a styrene-based monomer on the surface of the polystyrene-based resin particles. The resin particles are impregnated with a volatile foaming agent, and the resin particles are saturated and swelled in tetrahydrofuran (hereinafter referred to as 114931.doc -12·1325435 THF) at 25t: normal pressure. The thickness of the surface layer is in the range of 3 to just (four), and the gel component insoluble in THF is in the range of 10 to 50% by mass based on the total amount of the resin particles. The polystyrene-based resin constituting the portion other than the surface layer of the expandable polyphenylene-based resin particles of the present invention is not particularly limited, and examples thereof include styrene, CX-methylstyrene, and ethylene toluene. Homopolymerization of styrene monomer such as styrene, ethyl styrene, isopropyl styrene, dimethyl ethene
物或該等之共聚物等。X，構成粒種部分之聚苯乙婦系樹 脂，可為上述苯乙稀系單體與能和該苯乙料單體共聚的 乙稀基單體之共聚物’作為如此乙職單體，例如可例 舉：（甲基）丙賴η旨、（T基則酸乙3旨、（f基）丙稀酸 丁醋、（甲基）丙稀酸十六烧基醋等（曱基）丙稀酸院基醋， (甲基）丙烯腈、馬來酸二曱冑、富馬酸二甲自旨、富馬酸二 乙酯、富馬酸乙酯等。 又，構成上述表層之聚苯乙烯系樹脂，係使含由交聯性 單體的苯乙歸系單體聚合而形成。作為上述交聯性單體， 只要係可賦予發泡性聚苯乙稀系樹㈣子以交聯結構者， 則並無特別限定，例如可例舉：4烯基苯、聚乙二醇二 甲基丙稀酸㈣㈣基二醇二甲基丙烯㈣等之多官能性 :體等’纟中以二乙稀基苯為佳。又，構成樹脂表層之聚 本乙稀系樹脂’可為上述交聯性單體與上述苯乙稀系單體 以及能夠和該苯乙稀系單體共聚的乙稀基單體之共聚物， 作為如此乙稀基單體，例如可例舉：（甲基）丙烯酸甲醋、 (甲基）丙婶酸乙輯、（甲基）丙稀酸丁酿、（甲基）丙稀酸十六 114931.doc 1325435 烧基醋等（甲基）丙烯酸烷基酯，（甲基）丙烯腈、馬來酸二 甲酯、富馬酸二曱酯、富馬酸二乙酯、富馬酸乙酯等。 即，可於含有苯乙烯系單體、交聯性單體及聚合引發劑之 單體溶液中，供給上述乙烯基單體。 於本發明之發泡性苯乙烯系樹脂粒子中，上述表層厚度 為3〜100 μηι範圍、較好的是5〜8〇 μιη範圍、更好的是$〜川 μηι範圍、最好的是1〇〜5〇 μιη範圍。於該表層厚度小於3 μπι之情形時，發泡成形品之耐油性降低，含油分或色素或 界面活性劑等的液體易通過成形品而向外部滲出。另一方 面，於表層厚度大於100 μιη之情形時，2次發泡性降低從 而發泡粒子間之熔合率降低，且產生油分等滲出或者成形 品強度降低之問題。 上述表層厚度之測定方法之步驟，如圖1所示，較好的 是採用以下步驟：（1)M25°C、常壓下將樹脂粒子1浸潰於 THF中進行飽和膨潤化（參照圖1(a)) ; (2)繼而，將飽和膨 调化了的樹脂粒子2自THF中分離（參照圖1(b)) ; (3)繼而， 將已分離之樹脂粒子2浸潰於甲基丙稀酸曱醋（以下稱為 MMA)中（參照圖1(c))，以MMA置換經飽和膨潤化的樹脂 粒子2内部之THF(參照圖1(d)) ; (4)繼而，使MMA聚合而 製成聚曱基丙烯酸甲酯（以下，記做PMMA)固化體3，將樹 脂粒子以膨潤狀態固定於該PMMA固化體3中（參照圖 Ue)) ; (5)繼而，沿通過樹脂粒子中心之面將上述pmma固 化體3切斷（參照圖1(f)) ; (6)繼而，觀察該切斷面4，測量 樹脂粒子之表層厚度（參照圖1 (g))。 114931.doc -14- 1325435 圖2係依照上述測定方法製作的PMMA固化體3之剖面之 主要部分放大圖，該圖中符號5表示被固定之樹脂粒子之 表層’ 6表示粒子外部之PMMa相，7表示粒子内部之 PMMA相。 如圖2所示，藉由依序進行上述（1)〜（6)之步驟對本發明 之發泡性苯乙烯系樹脂粒子進行處理，而使表層5殘留於 PMMA固化體3之剖面上，能夠對其進行放大觀察以測定 $ 其厚度。 進而，相對於該樹脂粒子之總量，該發泡性苯乙烯系樹 脂粒子之不溶於THF之凝膠成分為1〇〜5〇質量％之範圍較 好的是15〜50質量％之範圍、更好的是15〜4〇質量％的範 圍。於該不溶於THF的凝膠成分小於10質量％之情形時， 所付發泡成形品之耐油性降低，因而含有油分或色素或者 界面活性劑等的液體易通過成形品向外部滲出。又，於不 各於THF的凝膠成分大於5G f量％之情形時在發泡成形 • 時預發泡粒子之間的熔合變差，不僅強度降低而且預發泡 粒子間的空隙增多，因而出現成形品的内容物易於滲出之 問題》 以下，就本發明之發泡性苯乙烯系樹脂粒子之製造方法 加以說明。 為了製造本發明之發泡性苯乙烯系樹脂粒子，而使用公 知的種聚合法（種子聚合法）。作為本發明中所使用之粒 種二可使用依照先前已知的苯乙烯系樹脂粒子製造方法而 獲得者。例如可例舉以下方法：於上述苯乙烯系單體中加 11493 丨.doc 15 1325435 入父聯性單體，再使其於水中進行懸浮聚合而製造聚苯乙 稀系樹脂粒種之方法；或者將苯乙稀系樹脂供給至擠出機 中’^行溶融混煉，且以股線狀或大體球狀自擠出機中擠 出，每隔特定長度進行切斷，從而製造苯乙稀系樹脂粒種 之方法等。就發泡成形性、物性之問題而言，上述苯乙烯 系樹脂粒子之重量平均分子量，較好的是15萬〜4〇萬、更 好的是25萬〜35萬。 作為本發明之解決課題，為了防止食品等中所含油分或 ㈣粉等色素滲出至外部，較好的是提昇發泡成形品表面 之耐油性。為了提昇以本發明之所謂珠粒法化“心法）之發 泡成形法而獲得的發泡成形品之耐油性，因發泡性苯乙烯 系樹脂粒子的表層常常暴露於發泡成形品的表面，故必須 提昇該樹脂粒子表面之交聯密度。進而，為了使該發泡性 苯乙烯系樹脂粒子保持優異之發泡成形性，較好的是，樹 脂粒子之中心部係由交聯密度盡可能低的苯乙烯系樹脂構 成。 繼而，將100質量份之上述粒種分散於水性介質中隨 後於該分散液中添加15〜100質量份之笨乙烯系單體以及 0.03〜1.0質量份之交聯性單體，使其被上述粒種吸收且使 其聚合而獲得苯乙烯系樹脂粒子，隨後使其浸潰易揮發性 發泡劑而製造發泡性聚苯乙烯系樹脂粒子。本發明之製造 方法之特徵為’將聚合過程中的成長粒子中之苯乙稀系樹 脂比例設為80〜1〇〇質量％之範圍，獲得發泡性苯乙烯系樹 脂粒子。以下’將成長過程中之粒種記做「成長粒種 114931.doc -16 - 1325435 本發明中，於上述聚合步驟中添加交聯性單體，較好的 疋，將苯乙烯系單體的一部分或全部溶解再添加交聯性單 體。如果單獨地添加交聯性單體及苯乙烯系單體，則於交 聯結構中產生不均，可能無法獲得均勻之發泡性苯乙烯系 樹脂粒子。 相對於粒種100質量份，將笨乙烯系單體之添加量設為 15〜100質量份之範圍。如果苯乙烯系單體小於15質量份， Φ 則所製成的發泡性苯乙稀系樹脂粒子之表層厚度較薄，從 而產生無法發揮充分耐油性之問題。又，若苯乙烯系單體 超過100質量份，則會過多地向粒種内滲透，因而所獲得 的發泡性苯乙烯系樹脂粒子之表層變得過厚，因此發泡能 力受損，粒子之間的黏合變弱，因而不僅内容物的油分自 粒子間滲出變多，而且產生成形品的強度亦降低之問題。 相對於粒種100質量份，將交聯性單體之添加量設定為 0·03 1·〇質量份之範圍。若交聯性單體小於〇 〇3質量份， • 則所製成的發泡性苯乙烯系樹脂粒子之表層之交聯結構不 足，因而產生無法發揮充分的耐油性之問題。另一方面， 若交聯性單體超過i.o質量份，則會過度交聯，因而存在 發泡能力受損、成形體之發泡粒子間隙變大、油分滲出増 加之問題。 作為使上述苯乙烯系單體吸收入粒種中而進行聚合時所 使用之聚合引發劑，並無特別限定，例如可例舉：過氧化 苯甲醯、月桂基過氧化物、過氧化苯甲酸第三丁酯、第三 丁基過氧化物、過氧化三曱基乙酸第三丁醋、過氧化異^ 114931.doc 1325435 基妷酸第二丁酯、過氧化乙酸第三丁酯、2,2-雙（第三丁基 過氧）丁烷、過氧化_3,3,5_三甲基己酸第三丁酯、過氧化六 氫對苯二甲酸二第三丁酯等有機過氧化物或者偶氮二異丁 腈、偶氮二（二甲基戊腈）等偶氮化合物等，可將該等單獨 使用或者多個併用。 作為上述聚合引發劑’較好的是，將用以獲得10小時半 衰期的分解溫度為50〇c以上且小於8〇(>c之聚合引發劑、與 鲁用以獲得ίο小時半衰期的分解溫度為8(rc〜12(rc之聚合引 發劑加以併用。再者，相對於苯乙稀系單體100質份，聚 〇引發劑之添加量，較好的是〇〇1〜3質量份。 、又，於上述分散液中’為了提昇笨乙烯系粒種及粒種之 分散穩定性，可添加懸浮穩定劑或穩定助劑。 作為上述懸浮穩定劑，例如可例舉：聚乙烯醇、甲基纖 維素、聚丙烯酿胺、聚乙婦料烧網等水溶性高分子，或 鱗酸約、焦鱗酸鎮等難溶性無機化合物。於使用難溶性益 鲁機化合物之情形時’通常併用陰離子界面活性劑。 作為如此陰離子界面活性劑，例如可例舉：月桂基硫酸 納等院基硫酸鹽、十二烧基苯續酸納等烧基苯續酸鹽、油 酸鈉等高級脂肪酸鹽' β_四羥基萘磺酸鹽等。 於本發明中，自聚合開始直至結束之期間，將聚合過程 。中的成長粒種中之苯乙料樹脂之含量維持於n⑽質量 %、較好的是85〜100質量％、更好的是9〇〜剛質量％之範 =。作為維持上述範圍之方法，可藉由反應系統的溫度、 本乙烯系單體的供給速度、聚合引發劑的量等來進行調 H493I.doc •18- 1325435 整。例如，反應溫度亦因聚合引發劑的種類而異，但較好 的疋80〜11〇。〇。其原因在於，若小於8〇〇c，則聚合速度會 變慢，因而苯乙稀系單體易滲入粒種内部，無法高效地於 表層進行交聯。又’若超過11Gt ’則所添加之苯乙稀系 單體會在被吸收入粒種之前進行聚合，使得向粒種之吸收 效率變差，成為無法使用之粉末狀，生產效率變差，故為 不好。 … • 成長粒種中之苯乙烯系樹脂之含量，可依下列方法進行 測定β 將乂里聚合反應中的成長粒種自聚合容器中取出，將其 肖水性彳質分離，隨後以紗布等除去成長粒種表面的水 分，製成測定樣品。 繼而，精密稱量0.08 g測定樣品，將其溶解於24mL曱苯 中。 於該溶解液中添加10 mL費氏試劑、3〇 mL25質量％碘 • 化_水溶液 '及約30 ‘之1質量％殿粉水溶液，以N/40硫 代硫酸鈉溶液進行滴定’求出樣品滴定數（Μ)。再者費 氏試幻係藉由將8.7 g雄及79 g三氯化峨溶解於2 l冰醋 酸中而製得。 另一方面，不溶解樣品而以與上述同樣方式進行滴定， 求出空白滴定數（mL)。 :而’依下式算出成長粒種中的苯乙烯系單體之含量。 苯乙稀系單體之含量（質量〇 1322χ(空白滴定數·樣 品滴定數）/測定樣品質量（g)。 114931.doc 1325435 所r敌媒開始直至聚合結束’以1〇分鐘間隔採取樣品，對 樣品進行上述操作，求出苯乙埽系單體之含量。 繼而，將成長粒子質量減去贫r < 長般錄質量減去本乙烯系單體量之量作為成 !粒種：的苯乙烯系樹脂之量，依下式算出成長粒子中的 本乙稀树脂含量（質量％)。 苯？婦系樹脂含量(質量％)=100x(測定樣品質量笨乙 婦系單體量）/測定樣品質量。 其次’使藉由上述種聚合而獲得的苯乙烯系樹脂粒子浸 潰易揮發性發泡劑，而製造發泡性苯乙稀系樹脂粒子。 作為上述易揮發性發泡劑，可使用通用者，例如可例 舉：丙烷、丁烷、戊烧等脂肪煙；u•二氣小氟乙烧 (HCFC-141b)、卜氣·u•二氟乙燒（HCFC i42b)、2_ 氣· m，2-四敦乙烷（HCFC_124)、u，12·四氟乙烷（HFc· 134a)、l，l-二氟乙烷（HFC _152a)等氤系發泡劑，較好的是 脂肪經。再者’易揮發性發泡劑，可單獨使用亦可併用。 進而，亦可於上述發泡性苯乙烯系樹脂粒子中，添加硫代 二丙酸酯、硫代二丁酸酯、伸乙基二硬脂醯胺等氣泡調整 劑、紫外線吸收劑、增量劑、著色劑等通用的添加劑。 發泡性苯乙烯系樹脂粒子之平均粒徑，可根據所得發泡 成形品的用途進行調整，但於發泡成形品係發泡成形容器 且厚度薄時’將其設為〇·2〜1 mm之範圍、較好的是設為 0.2〜0·8 mm、更好的是設為ο」〜0.7 mm，但並不限定於 此。 將如此獲得之發泡性苯乙烯系樹脂粒子，置於預發泡機 114931.doc •20- 1325435 中進行預發泡而製成預發泡粒子，將獲得的預發泡粒子填 充於發泡成形機的模内，隨後藉由加熱蒸氣等加熱介質使 其發泡，且藉由發泡壓使其相互熱熔合一體化，從而製成 具有期望形狀之發泡成形品。再者，預發泡粒子之堆積密 度’較好的是0.015〜0.20 g/cm3，但並不限定於此。 又，作為上述發泡成形品，可列舉各種形態者，就有效 發揮本發明之作用及效果而言’較好的是杯狀、碗狀、盤 • 狀、箱狀等之發泡成形容器》 於該發泡成形容器内，可容納：大豆油、菜籽油、紫蘇 油、橄欖油、芝麻油、紅花油、玉米油等植物油、牛油、 豬油、方便麵、燉品、蛋黃醬、沙拉調味汁、咖喱塊、黃 油、人造奶油、白色醬汁、人造酸乳類、冰淇淋、炸甜 圈、漢堡包、油炸雞等油性食品及脂肪食品、含有界面活 性劑的水溶液等。 如上所述，因上述發泡成形品係使特定的發泡性苯乙烯 • 系樹脂粒子發泡而獲得者，故發泡粒子之間在其等之界面 處牢固地熱熔合一體化，並且發泡粒子之間熱熔合之界面 部分之交聯密度變高，因而耐油性優異。 因此，即使於在發泡成形品内長期持續容納含油分的食 品或含咖喱粉等色素的食品、或者在發泡成形品内容納含 界面活性劑的液體等之情形時，發泡性粒子之間的熱熔合 界面亦不被油分、色素或界面活性劑等侵入，因此，可解 決油分或色素、含界面活性劑的液體等通過發泡粒子之間 的熱熔合界面滲出至發泡成形品外面之問題。進而，可獲 H4931.doc -21 - 1325435 得外觀漂亮、印刷性優異、強度等優異之發泡成形體。Or such copolymers and the like. X, a polystyrene resin constituting a seed portion, which may be a copolymer of the above styrene monomer and an ethylene monomer copolymerizable with the benzene monomer; For example, (meth) propylene η, (T-based acid B 3, (f-) butyl acrylate, (methyl) acrylic acid hexahydrate vinegar, etc. Acrylic acid based vinegar, (meth)acrylonitrile, diterpene maleate, dimethicone, diethyl fumarate, ethyl fumarate, etc. The styrene-based resin is formed by polymerizing a phenylethylene-containing monomer containing a crosslinkable monomer. The cross-linkable monomer can be imparted to the foamable polystyrene tree (four). The coupling structure is not particularly limited, and examples thereof include polyalkenyl groups such as 4-alkenylbenzene and polyethylene glycol dimethylpropionic acid (tetra)(tetra)diol dimethylpropene (tetra): Preferably, the diethyl benzene resin constituting the surface layer of the resin may be the crosslinkable monomer and the styrene monomer, and the styrene monomer The copolymer of the copolymerized ethylene monomer, as such a vinyl monomer, for example, methyl (meth)acrylate, (meth)propionic acid, and (meth)acrylic acid Stuffed, (meth)acrylic acid 16 114931.doc 1325435 alkyl methacrylate (meth) acrylate, (meth) acrylonitrile, dimethyl maleate, dinonyl fumarate, rich Diethyl maleate, ethyl fumarate, etc. That is, the vinyl monomer can be supplied to a monomer solution containing a styrene monomer, a crosslinkable monomer, and a polymerization initiator. In the foamable styrene-based resin particles, the surface layer has a thickness of from 3 to 100 μm, preferably from 5 to 8 μm, more preferably from 0 to 0.5 μm, most preferably from 1 to 5 Å. When the thickness of the surface layer is less than 3 μm, the oil resistance of the foamed molded article is lowered, and the liquid containing oil or a pigment or a surfactant is easily exuded to the outside through the molded article. On the other hand, in the thickness of the surface layer When it is larger than 100 μηη, the second expansion property is lowered and the fusion ratio between the foamed particles is increased. The method of measuring the thickness of the surface layer is as shown in Fig. 1. The step of measuring the thickness of the surface layer is as follows: (1) M25 ° C, resin under normal pressure The particles 1 are immersed in THF to be saturated and swelled (see Fig. 1 (a)); (2) the saturated and expanded resin particles 2 are separated from THF (see Fig. 1 (b)); Then, the separated resin particles 2 are immersed in methyl acetonate vinegar (hereinafter referred to as MMA) (see FIG. 1(c)), and the THF inside the saturated swelled resin particles 2 is replaced by MMA. (Fig. 1 (d)); (4) Next, MMA is polymerized to obtain a polymethyl methacrylate (hereinafter referred to as PMMA) cured body 3, and the resin particles are fixed in a swollen state to the PMMA cured body 3 (refer to Fig. Ue)); (5) Then, the pmma solidified body 3 is cut along the surface passing through the center of the resin particle (refer to Fig. 1 (f)); (6) Then, the cut surface 4 is observed, and measurement The surface layer thickness of the resin particles (refer to Fig. 1 (g)). 114931.doc -14- 1325435 Fig. 2 is an enlarged view of a principal part of a cross section of a PMMA cured body 3 produced by the above-described measuring method, in which the symbol 5 indicates that the surface of the resin particle to be fixed '6 indicates the PMMa phase outside the particle, 7 denotes the PMMA phase inside the particle. As shown in Fig. 2, the foamable styrene resin particles of the present invention are treated by the steps (1) to (6), and the surface layer 5 remains on the cross section of the PMMA cured body 3, which enables It is magnified to determine its thickness. Furthermore, the gel component of the styrene-based resin particles insoluble in THF is in the range of from 1 to 5 % by mass, preferably from 15 to 50% by mass, based on the total amount of the resin particles. More preferably, it is in the range of 15 to 4% by mass. When the gel component insoluble in THF is less than 10% by mass, the oil resistance of the foamed molded article to be reduced is lowered, so that a liquid containing an oil component, a coloring matter or a surfactant is easily bleed out to the outside through the molded article. In addition, when the gel component of each THF is larger than the amount of 5 G f, the fusion between the pre-expanded particles is deteriorated during the foam molding, and the strength is lowered and the voids between the pre-expanded particles are increased. The problem that the content of the molded article is likely to bleed out is described. Hereinafter, a method for producing the expandable styrene resin particles of the present invention will be described. In order to produce the expandable styrene resin particles of the present invention, a known seed polymerization method (seed polymerization method) is used. The particle 2 used in the present invention can be obtained by using a previously known method for producing styrene resin particles. For example, a method of producing a polystyrene resin particle by adding 11493 丨.doc 15 1325435 to the above-mentioned styrene monomer into a parent monomer and then suspending the polymerization in water; Alternatively, the styrene resin is supplied to the extruder to melt and knead, and extruded in a strand or a substantially spherical shape from the extruder, and cut at a specific length to produce styrene. A method of making a resin seed or the like. The weight average molecular weight of the styrene resin particles is preferably from 150,000 to 40,000, more preferably from 250,000 to 350,000, in terms of foam formability and physical properties. In order to prevent the oil contained in foods or the like or the dyes such as powder from oozing out to the outside, it is preferable to improve the oil resistance of the surface of the foamed molded article. In order to improve the oil resistance of the foamed molded article obtained by the foam molding method of the so-called bead method "heart method" of the present invention, the surface layer of the expandable styrene resin particles is often exposed to the foamed molded article. In addition, it is necessary to increase the crosslink density of the surface of the resin particles. Further, in order to maintain excellent foam formability of the expandable styrene resin particles, it is preferred that the center portion of the resin particles be a crosslink density. The styrene resin is formed as low as possible. Then, 100 parts by mass of the above-mentioned seed particles are dispersed in an aqueous medium, and then 15 to 100 parts by mass of a stupid vinyl monomer and 0.03 to 1.0 part by mass are added to the dispersion. The crosslinkable monomer is absorbed by the above-mentioned seed crystals and polymerized to obtain styrene resin particles, and then impregnated with a volatile foaming agent to produce expandable polystyrene resin particles. The manufacturing method is characterized in that the proportion of the styrene-based resin in the grown particles in the polymerization process is in the range of 80 to 1% by mass to obtain expandable styrene-based resin particles. The seed in the process is described as "growth seed 114931.doc -16 - 1325435. In the present invention, a crosslinkable monomer is added in the above polymerization step, preferably a ruthenium, and a part or all of the styrene monomer is dissolved. When a crosslinkable monomer and a styrene monomer are separately added, unevenness occurs in the crosslinked structure, and uniform foaming styrene resin particles may not be obtained. 100 parts by mass, the amount of the stupid vinyl monomer added is in the range of 15 to 100 parts by mass. If the styrene monomer is less than 15 parts by mass, Φ is the foamable styrene resin particles produced. The thickness of the surface layer is thin, and the problem of insufficient oil resistance is not obtained. Further, if the styrene monomer exceeds 100 parts by mass, it will excessively permeate into the seed, and thus the obtained expandable styrene resin Since the surface layer of the particles becomes too thick, the foaming ability is impaired, and the adhesion between the particles is weakened, so that not only the oil content of the contents permeates from the particles but also the strength of the molded article is lowered. Kind 10 0 parts by mass, the addition amount of the crosslinkable monomer is set to be in the range of 0·03 1·〇 part by mass. If the crosslinkable monomer is less than 3 parts by mass, • the foamable styrene thus produced The crosslinked structure of the surface layer of the resin particles is insufficient, and thus the problem of insufficient oil resistance is not obtained. On the other hand, if the crosslinkable monomer exceeds io by mass, excessive crosslinking occurs, and thus the foaming ability is impaired. The problem that the foaming particle gap of the molded article is increased and the oil is oozing out is not particularly limited, and the polymerization initiator used for the polymerization of the styrene-based monomer into the seed crystal is not particularly limited, and for example, : benzamidine peroxide, lauryl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxide, tridecyl acetic acid tributyl vinegar, peroxidation II 114931.doc 1325435 Dibutyl citrate, tert-butyl peroxyacetate, 2,2-bis(t-butylperoxy)butane, tert-butyl peroxy-3,3,5-trimethylhexanoate, Organic peroxide such as di-tert-butyl hexahydrophthalate or azobisisobutyl An azo compound such as a nitrile or azobis(dimethylvaleronitrile) may be used alone or in combination of two or more. As the above polymerization initiator, it is preferred that the decomposition temperature for obtaining a half-life of 10 hours is 50 〇c or more and less than 8 〇 (>c polymerization initiator, and the decomposition temperature for use in order to obtain an hour-half half-life) The polymerization initiator of 8 (rc~12 (rc) is used in combination. Further, the amount of the polyfluorene initiator to be added is preferably 1 to 3 parts by mass based on 100 parts by mass of the styrene monomer. Further, in the above dispersion, a suspension stabilizer or a stabilizer may be added in order to enhance the dispersion stability of the stupid ethylene seed and the seed. As the suspension stabilizer, for example, polyvinyl alcohol or a gel may be mentioned. Water-soluble polymers such as cellulose, polypropylene, amine, and polystyrene, or poorly soluble inorganic compounds such as scaly acid and pyrophyllin. When used in the case of poorly soluble Yilu compound, it is usually used together. An anionic surfactant. Examples of such an anionic surfactant include higher-grade fatty acid salts such as a sulfate-based sulfate such as sodium lauryl sulfate, a sodium benzoate such as sodium benzoate, and sodium oleate. 'β_tetrahydroxynaphthalene sulfonate, etc. In the present invention, the content of the styrene resin in the growing seed in the polymerization process is maintained at n (10)% by mass, preferably 85 to 100% by mass, more preferably 9 from the start to the end of the polymerization. The method of maintaining the above range is carried out by adjusting the temperature of the reaction system, the supply rate of the present vinyl monomer, the amount of the polymerization initiator, etc., to adjust the H493I.doc • 18-1325435 For example, the reaction temperature varies depending on the type of the polymerization initiator, but is preferably 疋80 to 11 〇. The reason is that if it is less than 8 〇〇c, the polymerization rate becomes slow, and thus the styrene is The monomer easily penetrates into the interior of the seed and cannot be cross-linked efficiently on the surface layer. If 'more than 11 Gt', the added styrene monomer will be polymerized before being absorbed into the seed, so that the absorption into the seed The efficiency is deteriorated and it becomes a powder that cannot be used, and the production efficiency is deteriorated, so it is not good. ... • The content of the styrene resin in the grown grain can be measured by the following method. Self aggregation The sample was taken out, and the water-based enamel was separated, and then the moisture on the surface of the grown seed was removed by gauze or the like to prepare a measurement sample. Then, 0.08 g of the measurement sample was accurately weighed and dissolved in 24 mL of toluene. Add 10 mL of Fischer's reagent, 3 mL of 255% by mass of iodine and _aqueous solution, and about 30% of the 1% by mass aqueous solution of the temple powder, and titrate with N/40 sodium thiosulfate solution to determine the sample titer ( Μ). Further, the Fahrenheit experiment was prepared by dissolving 8.7 g of male and 79 g of antimony trichloride in 2 l of glacial acetic acid. On the other hand, the sample was not dissolved and titrated in the same manner as above. The number of blank titrations (mL) was determined: and the content of the styrene monomer in the grown seed was calculated according to the following formula. Content of styrene monomer (mass 〇1322χ(blank titration·sample titration)/measurement sample mass(g). 114931.doc 1325435 The start of the r-energy until the end of the polymerization' takes samples at 1 〇 minute intervals, The sample was subjected to the above operation to determine the content of the phenelzine monomer. Then, the mass of the grown particles was subtracted from the lean < the mass of the long recording minus the amount of the monomer of the vinyl monomer as the pellet: The amount of the styrene resin is calculated by the following formula, and the content (% by mass) of the present ethylene resin in the grown particles is calculated. The content of the benzene-based maternity resin (% by mass) = 100 x (measurement sample mass of the stupid women) The mass of the sample is measured. Next, the styrene-based resin particles obtained by the above-described polymerization are impregnated with a volatile foaming agent to produce foamable styrene-based resin particles. A general-purpose person can be used, for example, fatty tobacco such as propane, butane or pentane; u•two-gas small fluoroacetone (HCFC-141b), Buqi·u•difluoroethane (HCFC i42b), 2_ Gas · m, 2-tetradane (HCFC_124), u, 12 · tetrafluoroethane (HFc· 134a), l,l-difluoroethane (HFC _152a) and other oxime foaming agents, preferably fat. In addition, 'volatile volatile foaming agent, can be used alone or in combination. Further, To the foamable styrene resin particles, a bubble adjusting agent such as thiodipropionate, thiodibutyrate or ethyl bis-stearylamine, a UV absorber, an extender, and a colorant are added. The average particle diameter of the foamable styrene resin particles can be adjusted according to the use of the obtained foamed molded article, but when the foamed molded product is molded into a foamed molded container and has a small thickness, it is set as The range of 〇·2 to 1 mm, preferably 0.2 to 0.8 mm, more preferably ο" to 0.7 mm, but is not limited thereto. The foamable styrene thus obtained Resin particles, pre-expanded in pre-expansion machine 114931.doc •20-1325435 to prepare pre-expanded particles, and the obtained pre-expanded particles are filled in the mold of the foam molding machine, followed by Heating a heating medium such as steam to foam it, and thermally fusing and integrating them with each other by foaming pressure In addition, the foamed molded article having a desired shape is preferably 0.015 to 0.20 g/cm 3 , but is not limited thereto. In the case of the shape and effect of the present invention, it is preferable that the foam molded container such as a cup shape, a bowl shape, a disk shape, or a box shape can be accommodated in the foam molded container. Vegetable oil such as soybean oil, rapeseed oil, perilla oil, olive oil, sesame oil, safflower oil, corn oil, butter, lard, instant noodles, stew, mayonnaise, salad dressing, curry block, butter, margarine, white sauce Oily foods such as juices, artificial yogurts, ice creams, doughnuts, hamburgers, fried chickens, fat foods, aqueous solutions containing surfactants, and the like. As described above, since the foamed molded article is obtained by foaming specific foamable styrene-based resin particles, the foamed particles are firmly thermally integrated and integrated at the interface between them, and foamed. The cross-linking density of the interface portion where the particles are thermally fused is high, and thus the oil resistance is excellent. Therefore, even in the case where the food containing the oil component or the food containing the pigment such as curry powder is continuously stored in the foamed molded article for a long period of time, or the liquid containing the surfactant is contained in the foamed molded article, the foaming particles are used. The thermal fusion interface is not invaded by oil, pigment, surfactant, etc., so that the oil component or the pigment, the surfactant-containing liquid, etc. can be oozing out through the heat fusion interface between the foamed particles to the outside of the foamed product. The problem. Further, it is possible to obtain a foam molded article having a beautiful appearance, excellent printability, and excellent strength, such as H4931.doc -21 - 1325435.
本發月之艮vm包裝體，係於含上述發泡成形品之發泡成 形夺器内包裝有油性食品或含有食用油脂與色素的食品 而成者。發泡成形容器内所填充食品之種類，只要係含油 脂者則並無特別限^ ’就有效發揮本發明之作用及效果而 言，較好的是如上述之含油脂的方便麵（包括輔料）、燉 品、蛋黃醫、沙拉調味汁、咖喱塊、黃油、人造奶油、白 色醬汁、人造酸乳類、冰淇淋、炸甜圈、漢堡包、油炸雞 等油性食品’或含食用油脂及色素之食品。該食品包裝體 之包裝形態’並無特別限定，可根據發泡成形品的形狀選 擇適當的包裝形態L於使用杯狀、碗狀、盤狀等之 發泡成形容器情形時，可製成於其容器内填充食品、且於 開口部封上蓋材料進行密封、進而根據需要以合成樹脂薄 臈等將整體進行包裝之形態。 本發明之食品包裝體，係於含上述發泡成形品之發泡成 形容器内包裝有油性食品或者含食用油脂與色素的食品而 成者，因即使於發泡成形容器内長期持續容納含油分 的食品或含咖喔粉等色素的食品，亦可防止油分或色素、 含界面活性劑的液體等通過發泡粒子之間的熱熔合界面滲 出至發泡成形容器外面之問題。 以下，根據實施例進行更詳細之說明，但本發明並不限 定於該等。 實施例 [實施例1] 11493l.doc •22· 1325435 士於裝備錢拌裝置之5 L高壓滅g器内，供給2』^離子 六、夂1600 g平均粒徑為0.3 mm且重量平均分子量為 萬之聚苯乙稀粒種、2〇 e隹絨舻雜 g焦磷酸鎂及1 g十二烷基苯磺 鈉，攪拌，製成分散液。The 艮vm package of this month is a food product containing an oily food or a food containing edible oils and fats in a foaming squirt containing the above-mentioned foamed molded article. The type of food to be filled in the foam-molded container is not particularly limited as long as it is fat-containing. In order to effectively exert the effects and effects of the present invention, it is preferred that the fat-containing instant noodles (including auxiliary materials) are as described above. , stew, egg yolk, salad dressing, curry block, butter, margarine, white sauce, artificial yogurt, ice cream, doughnuts, hamburger, fried chicken and other oily foods or containing edible oils and pigments food. The packaging form of the food package is not particularly limited, and an appropriate packaging form L can be selected according to the shape of the foamed molded article. When a foamed molded container such as a cup shape, a bowl shape, or a disk shape is used, it can be produced. The container is filled with a food, and a lid material is sealed on the opening, and the whole is packaged by a synthetic resin sheet or the like as needed. The food package of the present invention is obtained by packaging an oily food or a food containing edible oils and fats in a foam molded container containing the above-mentioned foamed molded article, because the oil content is continuously contained in the foamed molded container for a long period of time. The food or the food containing the pigment such as curry powder can also prevent the oil or the pigment, the liquid containing the surfactant, and the like from oozing out to the outside of the foamed shaped container through the heat fusion interface between the expanded particles. Hereinafter, the present invention will be described in more detail based on the examples, but the present invention is not limited thereto. EXAMPLES [Example 1] 11493l.doc •22· 1325435 In a 5 L high-pressure extinguisher equipped with a money mixing device, an average particle diameter of 0.3 mm and a weight average molecular weight of 2 ^ 6 ions, 夂1600 g were supplied. The polystyrene granules, 2 〇e 隹 舻 舻 g g magnesium pyrophosphate and 1 g sodium dodecyl benzene sulfonate were stirred to prepare a dispersion.
將Mg料交聯性單體之二乙稀基苯、2〇g過氧化 醯（10小時半哀期為74〇c)及丨〇 g過氧化苯甲酸第三丁酯（1〇 小時半衰㈣104°c)溶解於彻g苯乙烯單體中，添加所獲 仔之物質且以均質攪拌器攪拌使其乳濁，製成苯乙烯： 繼而將_L述分散液保持於9〇〇c，於該分散液中用1 5小 時連續供給上述苯乙烯溶液。其後，於啊下進—步保持 1小時，隨後升溫至125。(：保持丨小時，結束聚合。 '、 測定該聚合過程中成長粒種中之苯乙烯系樹脂之比例。 其結果，成長粒子中之樹脂之最少比例為88〇/〇。 其後，於丨25。〇下保持原樣，供給u〇 §正戊烷、3〇 §異 戊烷，再連續保持3小時其後，用2小時冷卻至3〇。〇，除 去分散介質，進行絲、乾燥，獲得發泡性聚苯乙稀系樹 脂粒子。 對獲得之發泡性苯乙烯系樹脂粒子，實施（1)表層厚度之 測定、以及（2)不溶於THF的凝膠成分之測定。 (1)表層厚度之測定為：（a)自獲得之發泡性苯乙烯系樹脂 粒子中挑選直徑為0.3〜0.4 mm者，精密稱量1〇〇 g，將其 浸潰於100 ml之THF中； (b)浸潰後，於25°C、大氣壓條件下放置24小時，使其於 114931.doc •23· 1325435 THF中餘和膨潤； (c)24小時後，用8〇網目之金屬網進行過濾，獲得膨潤樹脂 粒子； ml之市售 (d)於可密閉之外徑17 mm、長1〇5 mm、容量1〇 的》式•中’於使上述膨潤樹脂粒子膨潤之狀態下，添加2 g該膨潤樹脂粒子、3 g MMA、〇 〇〇3 §之2,2•偶氮二（2,4_二 甲基戊腈），將膨潤樹脂粒子浸潰於MMA中；Diethylated benzene of the cross-linking monomer of Mg, 2 〇g of ruthenium peroxide (74 〇 c for 10 hours and half mourning) and butyl butyl peroxybenzoate (1 〇 half-life) (4) 104 ° c) dissolved in the styrene monomer, added to the obtained material and stirred with a homomixer to make it emulsified to make styrene: and then the _L described dispersion is maintained at 9 〇〇 c, The above styrene solution was continuously supplied to the dispersion for 15 hours. Thereafter, the process was continued for 1 hour, and then the temperature was raised to 125. (: The polymerization was terminated after keeping the temperature for a while. ', The ratio of the styrene resin in the grown seed during the polymerization was measured. As a result, the minimum ratio of the resin in the grown particles was 88 〇 / 〇. Thereafter, in 丨 25 Keep the original as it is, supply u〇§ n-pentane, 3〇§ isopentane, and keep it for 3 hours, then cool it to 3〇 in 2 hours. 〇, remove the dispersion medium, silk, dry, get hair The foamable styrene-based resin particles are subjected to (1) measurement of the surface layer thickness and (2) measurement of the gel component insoluble in THF. (1) Surface layer thickness The measurement is as follows: (a) selecting a diameter of 0.3 to 0.4 mm from the obtained expandable styrene resin particles, accurately weighing 1 〇〇g, and immersing it in 100 ml of THF; (b) After impregnation, it was allowed to stand at 25 ° C under atmospheric pressure for 24 hours, and allowed to swell in 114931.doc •23· 1325435 THF; (c) 24 hours later, it was filtered with a metal mesh of 8 mesh. Swelling resin particles; commercially available in ml (d) at a sealable outer diameter of 17 mm and a length of 1 mm 5 mm In the state in which the above-mentioned swelling resin particles are swollen, 2 g of the swelling resin particles, 3 g of MMA, 〇〇〇3 § 2, 2 azo 2 (2, 4 _) are added. Dimethyl valeronitrile), immersing the swelled resin particles in MMA;
(e)以40。(：之恆溫槽，於密閉狀態下將上述厘厘八浸潰物加 熱20小時； (0加熱後，以冷水冷卻，以不變形之方式自試管中取出聚 合過程中之PMMA ; (g) 以切刀沿通過固定於内部之樹脂粒子中心之面，切削所 獲得之聚合過程中之PMMA ; (h) 以70 C的烘箱將所切得之物質進行2小時再加熱； (0再加熱後，以電子顯微鏡測定pMMA固化體内之樹脂粒 子之表層厚度； ϋ)將於ίο處測定之數值之平均值作為表層厚度（μιη)。 實施例1之發泡性聚苯乙烯系樹脂粒子的表層厚度之測 定結果為1 5 μιη。 (2)不溶於THF之凝膠成分之測定 不溶於THF之凝膠成分’係以以下條件所測定之值。 於25°C、常壓下，將發泡性聚苯乙烯系樹脂粒子之測定 樣品W!(精密稱量1.00 g±0.02 g)於1〇〇 之THF中浸潰24 小時。浸潰後用80網目的金屬網進行過濾，將殘渣於8〇〇c H4931.doc •24· 1325435 cmHg之壓力進行2小時減壓乾燥。乾燥後置於乾 燥器内自然冷卻至室溫，測定乾燥殘渣之質量w2。 依下式由上述測定值算出不溶於THF之凝膠成分。 不溶於THF之凝膠成分（質量％)= 1〇〇xW2/Wi 實轭例1之發泡性聚苯乙烯系樹脂粒子的不溶於丁的 凝膠成分之測定結果為32質量％。 進而，將所獲得之發泡性聚苯乙烯系樹脂粒子進行發泡 _ A Μ #所獲知之發泡成形品實施以下評價：⑺成形品炫 合率之測定、以及（4)防止油分滲出性能之評價。 首先，以下列條件將發泡性聚苯乙烯系樹脂粒子進行發 泡成形，製成發泡成形容器。 於1·〇 kg發泡性苯乙烯系樹脂粒子令加入3 §硬脂酸辞 (粉碎品平均最大長度為2〇μιη)，於高速流動型混合機内 攪拌2分鐘。其次，供給！找乙二醇，進而攪拌2分鐘且 以硬脂酸鋅進行包覆。其後，於暗冷處保存3天。 • 之後，將上述發泡性笨乙烯系樹脂粒子供給至預發泡機 中’用水蒸氣使其預發泡至堆積密度為Q1 g/em3，而獲得 預發泡粒子。將該預發泡粒子於常溫下保存丨天，將其乾 燥。 其次，將上述預發泡粒子供給、填充入發泡成形機内的 成形模内，用0.20 MPa水蒸氣對預發泡粒子進行6秒鐘持 續加熱，使其發泡，獲得内部容積為45〇 cm3且壁厚為2 mm之杯狀發泡成形容器。再者，杯狀之發泡成形容器， 係自平面圓形狀底面部的外周緣向斜上方突出設置具一定 114931 .doc -25· 1325435 高度之周壁部而成者。 (3) 成形品熔合率之測定 所獲得之發泡成形容器的發泡粒子間之熔合率（成形品 熔合率）’係依下列方法進行測定。 用手將上述發泡成形容器之侧壁分成兩半，對於其剖面 中之發泡粒子，將粒子内破裂的粒子數（a)及於粒子間的界 面處破裂的粒子數（b)進行計數，代入式[(a)/((a) + (b))]X 1 〇〇中，將所獲得之值作為熔合率（％)。以下述評價 方法進行評價。 ◎…熔合率為80%以上’成形品溶合率極佳。 〇··.溶合率為50%以上小於80% ’成形品熔合率良好。 X···熔合率小於50%，成形品熔合率差。 實施例1之發泡成形容器中之成形品熔合率為9〇%，評 價測定結果為◎。 (4) 防止油分滲出性能之評價 於所獲得之發泡成形容器（内容積為45〇 cm3)内將市售 方便麵（咖喱味）中所使用之含咖喱粉的調味料及辅料置入 容器達容器體積的80%(容積360 cm3)，再以市售的食品用 包覆膜來包裝容器整H ’將It包農容器置於保持於^之 烘箱内，再測定咖喱油脂成分滲出至包裝容器外面之時 間。 依下述評價方法來評價防止油分滲出性能。 防止油分 ◎…經過48小時後’咖喱油脂成分並未滲出 滲出性能極佳。 114931.doc -26- 1325435 於48小時内，有咖喱油脂成分滲 〇···在24小時以上小 出，防止油分滲出性能良好 X".在不足24小時内， 滲出性能差。 /由脂成分滲出，防止油分 實施例1之發泡成形容 測定結果為◎。 ° 枝油分滲出性能之評價之 該等結果示於表1。 [實施例2] 其餘以與實 除連續供給2.0小時笨乙烯單體溶液以外 施例1同樣之操作順序進行。結果示於表卜 [實施例3] 其餘以與實 除連續供給G. 5小時笨乙料體溶液以外 施例1同樣之操作順序進行。結果示於表卜 [實施例4] 除將1720 §聚笨乙稀粒種、U g二乙稀基苯、i.3 g過氧 化本甲酿及0 · 3 g過氣 卜'^田故你 g軋化本甲酸第三丁酯溶解於280 g苯乙 蝉單體中而製成苯乙烤溶&， χ 夜以及用1 ·5小時供給苯乙烯 溶液以外，其餘以與實施例i同樣之操作順序進行。結果 示於表1。 [實施例5] 除將劃g聚苯乙烯粒種、2 8 g二乙稀基苯、3 化苯曱醯及0.8 g過氧化笨甲酸第三丁醋溶解於 彿單體中而製成笨乙稀溶液，以及用2〇小時供給笨 溶液以外，其餘以與實施例i同樣之操作順 % 。結果 U4931.doc •27- 1325435 示於表1。 [實施例6] 除將1050 g聚苯乙烯粒種、3.3 g二乙烯基苯、4.4 g過氧 化笨曱醯及0.95 g過氧化苯甲酸第三丁酯溶解於950 g苯乙 缔單體中而製成苯乙烯溶液，以及用3.0小時供給苯乙烤 溶液以外’其餘以與實施例1同樣之操作順序進行。結果 示於表1。 [比較例1 ] 除不使用二乙烯基苯以外，其餘以與實施例1同樣之操 作順序進行❶結果示於表1。 [比較例2] 除用4小時供給苯乙烯溶液以外，其餘以與實施例1同樣 之操作順序進行。結果示於表1。 [比較例3] 除將1800 g聚苯乙烯粒種、〇 7 g二乙烯基苯、1〇 g過氧 化本甲酿及0.2 g過氧化苯甲酸第三丁醋溶解於2〇〇 g苯乙 歸單體中而製成苯乙婦溶液，以及用1.5小時供給笨乙稀 溶液以外’其餘以與實施例1同樣之操作順序進行。結果 示於表1。 [比較例4] 除將1〇5〇 g聚苯乙烯粒種、3 3 g二乙烯基苯、4 6 g過氧 化笨甲醯及1.0 g過氧化苯甲酸第三丁酯溶解於95〇 g苯乙 烯單體中而製成笨乙烯溶液，以及用10小時供給苯乙烯 溶液以外，其餘以與實施例丨同樣之操作順序進行。結果 示於表1。 II4931.d〇, -28- 1325435(e) to 40. (: the constant temperature bath, the above-mentioned PCT occupant is heated in a sealed state for 20 hours; (0 after heating, cooled with cold water, the PMMA in the polymerization process is taken out from the test tube without deformation; (g) The cutter cuts the PMMA in the polymerization process obtained by passing through the center of the resin particle fixed inside; (h) the cut material is heated in a 70 C oven for 2 hours; (0 after reheating, The surface layer thickness of the resin particles in the pMMA-cured body was measured by an electron microscope; 平均值) The average value of the values measured at ίο was taken as the surface layer thickness (μιη). The surface layer thickness of the expandable polystyrene-based resin particles of Example 1. The measurement result was 15 μm. (2) Measurement of gel component insoluble in THF The gel component insoluble in THF was measured by the following conditions. The foaming property was measured at 25 ° C under normal pressure. The measurement sample of the polystyrene resin particles W! (precisely weighed 1.00 g ± 0.02 g) was immersed in 1 THF for 24 hours. After the impregnation, it was filtered with a mesh of 80 mesh, and the residue was placed at 8 Torr. 〇c H4931.doc •24· 1325435 cmHg pressure for 2 hours minus After drying, it was placed in a desiccator and naturally cooled to room temperature, and the mass w2 of the dried residue was measured. The gel component insoluble in THF was calculated from the above-mentioned measured value according to the following formula. The gel component insoluble in THF (% by mass) = The result of measurement of the gel component of the foam-insoluble polystyrene resin particle of the 1 〇〇xW2/Wi yoke 1 was 32% by mass. Further, the obtained expandable polystyrene resin was obtained. The foamed molded article obtained by foaming _ A Μ # was subjected to the following evaluations: (7) measurement of the shrinkage ratio of the molded article, and (4) evaluation of the oil bleed resistance. First, the expandable polyphenylene was subjected to the following conditions. The vinyl resin particles are foam-molded to form a foam-molded container. The foaming styrene resin particles of 1·〇kg are added to 3 § stearic acid (the average maximum length of the ground product is 2〇μιη). The mixture was stirred for 2 minutes in a high-speed flow type mixer. Next, supply! Find ethylene glycol, stir for 2 minutes, and coat with zinc stearate. Thereafter, store in a dark place for 3 days. • After that, foam the above. Stupid vinyl resin particles are supplied to In the pre-foaming machine, 'pre-expansion with water vapor to a bulk density of Q1 g/em3 to obtain pre-expanded particles. The pre-expanded particles are stored at room temperature for a few days, and dried. The pre-expanded particles were supplied and filled in a molding die in a foam molding machine, and the pre-expanded particles were continuously heated with 0.20 MPa of water vapor for 6 seconds to be foamed to obtain an internal volume of 45 〇cm 3 and a wall thickness of a 2 mm cup-shaped foam-molded container. Further, the cup-shaped foam-molded container is provided with a peripheral wall portion having a height of 114931 .doc -25· 1325435 from the outer peripheral edge of the bottom surface portion of the flat circular shape. Adult. (3) Measurement of the fusion rate of the molded article The fusion ratio (molding ratio of the molded article) between the expanded beads of the obtained foam molded container was measured by the following method. The side wall of the above-mentioned foam-molded container is divided into two halves by hand, and the number of particles broken in the particle (a) and the number of particles broken at the interface between the particles (b) are counted for the expanded particles in the cross section. In the substitution formula [(a) / ((a) + (b))] X 1 〇〇, the obtained value is taken as the fusion ratio (%). The evaluation was carried out by the following evaluation method. ◎ The fusion ratio is 80% or more The molded article has an excellent fusion ratio. 〇··. The dissolution rate is 50% or more and less than 80% ‘The molded article has a good fusion rate. The fusion rate of X··· is less than 50%, and the fusion rate of the molded article is poor. The molded product of the foam molded container of Example 1 had a fusion ratio of 9 % by weight, and the evaluation result was ◎. (4) Evaluation of the prevention of the oil oozing performance The curry powder-containing seasonings and auxiliary materials used in the commercially available instant noodles (curry flavor) were placed in the container to the container in the obtained foamed molded container (the inner volume was 45 〇cm3). 80% of the volume (volume 360 cm3), and then packaging the container with a commercially available coating film for food. H' Place the container of the Itanban in an oven kept in the oven, and then measure the exudation of the curry oil and fat to the outside of the packaging container. Time. The prevention of oil bleed out performance was evaluated by the following evaluation method. Preventing oil ◎... After 48 hours, the curry oil and fat components did not ooze out. The bleed out performance was excellent. 114931.doc -26- 1325435 In 48 hours, there is a curry oil component infiltration 〇···Small in 24 hours or more to prevent oil oozing performance. X". In less than 24 hours, the bleed performance is poor. / oozing out from the fat component to prevent oil. The foaming molding capacity of Example 1 was measured as ◎. ° Evaluation of branch oil bleed performance These results are shown in Table 1. [Example 2] The rest was carried out in the same operation procedure as in Example 1 except that the continuous supply of the stupid ethylene monomer solution for 2.0 hours was carried out. The results are shown in Table 3. [Example 3] The rest was carried out in the same operation procedure as in Example 1 except that the G. 5-hour stupid solution was continuously supplied. The results are shown in Table [Example 4] except that 1720 § polystyrene, U g diphenyl benzene, i.3 g peroxide, and 0 · 3 g gas The g-butyl butyl methacrylate is dissolved in 280 g of phenethyl hydrazine monomer to make styrene bromide &amp; night and the styrene solution is supplied for 1.5 hours, and the rest is the same as in the example i The same sequence of operations is performed. The results are shown in Table 1. [Example 5] In addition to dissolving polystyrene seed, 28 g of diethylbenzene benzene, benzoin and 0.8 g of tributyl acetonate, which was dissolved in a monomer, was made stupid The same operation as in Example i was carried out except that the ethylene solution was supplied to the solution in an amount of 2 hours. Results U4931.doc •27-1325435 is shown in Table 1. [Example 6] In addition to 1050 g of polystyrene seed, 3.3 g of divinylbenzene, 4.4 g of alum, and 0.95 g of butyl peroxybenzoate were dissolved in 950 g of styrene monomer The same procedure as in Example 1 was carried out except that a styrene solution was prepared and the mixture was supplied with a benzene b-baked solution for 3.0 hours. The results are shown in Table 1. [Comparative Example 1] The results are shown in the same procedure as in Example 1 except that divinylbenzene was not used. The results are shown in Table 1. [Comparative Example 2] The same procedure as in Example 1 was carried out except that the styrene solution was supplied over 4 hours. The results are shown in Table 1. [Comparative Example 3] In addition to dissolving 1800 g of polystyrene seed, 〇7 g of divinylbenzene, 1 〇g of peroxidized broth and 0.2 g of benzoic acid benzoic acid, butyl ketone was dissolved in 2 g of styrene The same procedure as in Example 1 was carried out except that the styrene solution was prepared as a monomer and the solution was supplied to the stupid ethylene solution for 1.5 hours. The results are shown in Table 1. [Comparative Example 4] In addition to 1 〇 5 〇 g of polystyrene seed, 3 3 g of divinyl benzene, 4 6 g of benzoic acid, and 1.0 g of tert-butyl peroxybenzoate were dissolved in 95 〇g The styrene monomer was used to make a stupid ethylene solution, and the styrene solution was supplied for 10 hours, and the same procedure was carried out in the same manner as in Example 。. The results are shown in Table 1. II4931.d〇, -28- 1325435
【II 油分滲出 防止性能 ◎ ◎ ◎ ◎ ◎ ◎ X X X X 成形品 熔合率 (質量％) ◎ ◎ ◎ ◎ ◎ o ◎ ◎ 〇 X 不溶於THF之凝 膠成分 (質量％) (Ν m in m t-H 浮 o ON 00 ㈣： ^ v〇 Ο 寸 cn m os 1 o t-H W ^ Co' 伽 1 «U 〇、 ^ 1〇Η Ϊ _ 1$ ^ oo 00 v〇 Os s m On m 00 00 ss oo Q\ in amt /*—s 5 傘 難》Η S s g o g o g o 〇 m CN o CN m o 碟 g o s o <N m O 苯乙烯系 單體 (質量份） in <N ^T) <N in (N v〇 ίο <N CN o κη σ\ 種樹脂量 (質量份） o o 〇 o o 〇 〇 o o o o o o o o o o ο ο 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 比較例1 比較例2 比較例3 1比較例4 114931.doc -29- 1325435 由表1之結果可瞭解，本發明之實施例1〜6之發泡性聚苯 乙烯系樹脂粒子及使用其製造之發泡成形容器，具有優異 之成形品熔合率及防止油分滲出性能。 另一方面，不使用交聯性單體之比較例1中所獲得之發 泡成形容器之防止油分滲出性能差。 又，表層厚度為1 μπι且小於本發明中的表層厚度的範圍 之比較例2和3之發泡成形容器之防止油分滲出性能差。 進而’表層厚度為110 μιη且厚度大於本發明中的表層厚 度範圍之比較例4之成形品熔合率及防止油分滲出性能亦 差。 【圖式簡單說明】 圖l(a)-(g)係表示測定發泡性聚苯乙烯系樹脂粒子之表 層厚度之操作順序之概要構成圖。 圖2係表示固定於PMMA固化體上之樹脂粒子之表層之 放大圖。 【主要元件符號說明】 1、2 樹脂粒子 3 PMMA固化體 4 剖面 5 表層 6 粒子外部之PMMA相 7 粒子内部之PMMA相 114931.doc -30-[II] Oil oozing prevention performance ◎ ◎ ◎ ◎ ◎ ◎ XXXX Molding rate of molded product (% by mass) ◎ ◎ ◎ ◎ ◎ o ◎ ◎ 〇X Gel component insoluble in THF (% by mass) (Ν m in m tH float o ON 00 (4): ^ v〇Ο inch cn m os 1 o tH W ^ Co' 伽 1 «U 〇, ^ 1〇Η Ϊ _ 1$ ^ oo 00 v〇Os sm On m 00 00 ss oo Q\ in amt /*—s 5 Umbrella Difficulty Η S sgogogo 〇m CN o CN mo Dish goso <N m O Styrene monomer (parts by mass) in <N ^T) <N in (N v〇ίο < N CN o κη σ\ Kind of resin amount (parts by mass) oo 〇oo 〇〇oooooooooo ο 例 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 1 Comparative Example 4 114931.doc -29- 1325435 It is understood from the results of Table 1 that the expandable polystyrene resin particles of Examples 1 to 6 of the present invention and the foam molded container produced using the same have excellent formation. The fusion rate of the product and the prevention of the oil bleed out performance. On the other hand, the foam molding obtained in Comparative Example 1 in which the crosslinkable monomer was not used The container was found to have poor oil bleed resistance. Further, the foamed molded containers of Comparative Examples 2 and 3 having a surface layer thickness of 1 μm and less than the surface layer thickness in the present invention were inferior in preventing oil bleed out. Further, the surface layer thickness was 110 μm. The molded article fusion ratio and the prevention of oil bleed out property of Comparative Example 4 having a thickness larger than the thickness range of the surface layer in the present invention are also inferior. [Simplified Schematic Description] Figs. 1(a)-(g) show the measurement of foaming polyphenylene. Fig. 2 is an enlarged view showing the surface layer of the resin particles fixed on the PMMA cured body. [Description of main components] 1. 2 Resin particles 3 PMMA cured body 4 Section 5 Surface layer 6 PMMA phase outside the particle 7 PMMA phase inside the particle 114931.doc -30-