200938572 六、發明叙明： 【發明所屬之技術領域】 本發明係關於〜錄 方法，該粒子係使用於^性聚苯乙稀系樹脂粒子的製造 衝材之聚苯乙缔系樹月旨發__ : 發明係有關於—種發泡性聚笨乙稀系樹脂粒子的=方本 法，其於成形時所使用>a佴亍旳1造方 ❹ 得到外觀美麗且具有二氣的壓力即使為低壓，亦可 成形，故在成形步驟中^度之發泡成形體，由於可低壓 本案係依據2_年77短每一發射之成形時間。 2008-19000號主張優先 1日於日本所申請之特願 【先前技術】 援職 膠係::用容器或捆包、緩衝材所使用之發泡塑 烯糸樹脂發泡成形體。之隶本乙 ❹ 體的制I :業上所進行之聚苯乙烯系樹脂發泡成形 烯系ί脂粒子薪^含有揮發性發泡劑等之發泡性聚苯乙 :曰θ瘵氣等熱媒體進行加熱’並進行發泡(預備 發泡）至所希望之體密产 货巴u*貝備 粒子填充於具有構成二a—)後，將此預備發泡 成形模的該模Ϊ = = :形形狀的模穴(一 轨媒體進彳預備發泡粒子藉蒸氣等 :體加熱而進行模内發泡成形，成為發泡成形體。 盥苟播路得到之聚苯乙稀系樹脂發泡成形體的密度係成為 -、、A之體讀幾乎相同。體密度的設定係依聚笨乙 320980 200938572 烯系樹脂發泡成形體所要求之強度'與發泡性聚苯乙烯系 樹脂粒子所具有之發泡性能來決定。例如，於家電品等之 捆包材或魚箱等食品容器所使用之聚苯乙烯系樹脂發泡成 形體，係以約0. 02至0. 017g/cm3之密度者供給至市場。 在此成形步驟中，發泡成形體之外觀或強度係依蒸氣 等加熱媒體溫度（當其為水蒸氣時，則為加熱蒸氣壓力）而 變化。例如，以水蒸氣進行加熱時，若提高加熱壓力，則 成形體之外觀或強度有提昇之傾向，但因冷卻時間變長， 生產性降低，故不佳。 ❹ 更進一步，若加熱壓力變高，則發泡成形體之表面受 熱熔融，導致發泡成形體之外觀變差。 反之，若降低加熱壓力而成形，則雖然每一發射之成 形時間變短，但預備發泡粒子間之接著變弱，發泡成形體 之外觀、強度變差。 如此，在成形步驟中之蒸氣的加熱蒸氣壓從低壓至高 壓，可某程度自由地成形，係發泡性聚苯乙烯系樹脂粒子 ◎ 的重要特性之一。 一般而言，在聚苯乙烯系樹脂發泡成形體之製造中， 每一發射之成形時間與發泡成形體之強度的關係，當成形 時間為長時，可得到具有高強度之發泡成形體，反之，成 形時間短時，可看到發泡成形體的強度有降低之傾向。 用以縮短聚苯乙烯系樹脂發泡成形體之成形時間的習 知技術，可舉例如專利文獻1至5。 於專利文獻1中已提出一種於發泡性聚苯乙烯系樹脂 4 320980 200938572 粒子之表面被覆在常溫下為固體且為6〇網 狀脂肪族親與脂職醇之㈣方法。 X下之粉末 時間中大幅縮短冷卻時間，而在成形時間之=可在成形 效，但有伴隨強度降低之倾向。 ㈤知方面报有 又，於專利文獻2中心石壤的乳液，專 提出流動石蟻，專利文獻 料文獻3中 化合物，專利讀”提啊 ❹ 糸樹絲子紐錄子表面之方法。，1乙稀 無法^免作為發泡成形體時之強度的降低。4之方法亦 [先刖技術文獻] [專利文獻] [專利文獻1] [專利文獻2] [專利文獻3] [專利文獻4] ❹[專利文獻5] 【發明内容】 日本特公昭58-56568號公報 日本特開昭δ(Μ95135號公報 日本特開昭5Μ35969號公報 曰本特開昭52165號公報 日本特開昭59-202235號公報 [發明欲解決之課題] 其於成形時所使用之水蒸氣的壓力 γ .，、、，亦可得到外觀美麗且具有高的強度之發泡成 形體由於可低壓成形，故在成形步驟中，可使每1發射 之成形時間縮短。 [用以解決課題之手段] 320980 200938572 為了達成前述目的，本發明提供一種發泡性聚苯乙烯 系樹脂粒子之製造方法，其係進行如下之步驟而得到發泡 性聚苯乙烯系樹脂粒子： (1) 第1聚合步驟：於水中分散聚苯乙烯系樹脂種粒子而成 之分散液中，相對於聚苯乙烯系樹脂種粒子100質量份供 給苯乙烯系單體7. 0至80. 0質量份與丙烯酸酯系單體2. 0 至12. 0質量份，使種粒子吸收此等單體，並聚合而使聚苯 乙稀糸樹脂種粒子成長； (2) 第2聚合步驟：然後，於該分散液中只供給苯乙烯系單 體，使種粒子吸收該單體，並聚合而使聚苯乙烯系樹脂種 粒子成長；以及 (3) 含浸發泡劑的步驟：在進行第2聚合步驟而製造聚苯乙 烯系樹脂粒子之後、或在聚苯乙烯系樹脂粒子之成長中 途，含浸發泡劑。 又，本發明係提供一種發泡性聚苯乙烯系樹脂粒子， 其係含有苯乙烯系單體與丙烯酸酯系單體之共聚物，其特 徵在於： 在藉ATR法紅外線分光分析以分析前途發泡性聚苯乙 烯系樹脂粒子之表面所得到之紅外線吸收光譜中，求出在 1730CHT1之吸光度D1730與1600CHT1之吸光度D1600後，從 D1730/D1600所算出之吸光度比（A);與 在藉ATR法紅外線分光分析以分析前途發泡性聚苯乙 烯系樹脂粒子之中心部所得到之紅外線吸收光譜中，求出 在1730CHT1之吸光度D1730與1600cm1之吸光度D1600後， 6 320980 200938572 . 從D1730/D1600所算出之吸光度 . 係滿足（A)<(B)，且（A)為0· 〇5以上之關係。 於前述發泡性聚苯乙烯系樹塒粒子，前述吸光度比（ 宜為0. 05至0.50之範圍内，且前述吸光度比（B)宜為〇 至0· 60的範圍内。· 於前述發泡性聚苯乙烯系樹月旨粒子，前述吸光度 與（B)之比（B/A)宜為1.10至3. 0〇的範圍内。 冑述發泡性聚苯乙婦系樹赌麵子，宜為依前述發泡性 11聚苯乙烯系樹脂粒子之製造方法所得到者。 又’本發明係提供-種預備發泡粒子，其係使前迷 泡性聚苯乙稀系樹脂粒子以體密度成為〇. 至〇. 〇33VM 的範圍之方式進行預備發泡所得到者。 又’本發明係提供-種發泡成形體，其係使前迷 發泡粒子填充於成形模之模穴内，藉由加熱龙進行模 泡成形所得到者。 ^ ❹[發明之效果] 本發明之發泡性聚苯乙烯系樹月旨粒子，於成形時所使 ^水蒸氣的壓力即使為健，亦可得财觀美麗且具有 间的強度之發泡成形體。 言的明，/p可得到一種發泡成形體，其即使在以 :、療乳S成形時，亦不易因耐 低 成形體 外觀的劣化。 件，可提供一種發泡成形體κ成形的條 件乾圍非常廣，滿足各種成形時所希望之品質。 320980 7 200938572 本發明之發泡性聚苯乙烯系樹脂粒子及預備發泡粒子 係相較於習知品，發泡性能之經時變化變少，即使在長期 保存後，亦相較於習知品具有更充分的發泡性能，保存性 優異。 【實施方式】 本發明之發泡性聚苯乙烯系樹脂粒子之製造方法，係 進行如下之步驟而得到發泡性聚苯乙烯系樹脂粒子： (1) 第1聚合步驟：於水中分散聚苯乙烯系樹脂種粒子而成 之分散液中，相對於聚苯乙烯系樹脂種粒子100質量份供 給苯乙烯系單體7. 0至80. 0質量份與丙烯酸酯系單體2. 0 至12. 0質量份，使種粒子吸收此等單體，並聚合而使聚苯 乙烯系樹脂種粒子成長； (2) 第2聚合步驟：然後，於該分散液中只供給苯乙烯系單 體，使種粒子吸收該單體，並聚合而使聚苯乙烯系樹脂種 粒子成長；以及 (3) 含浸發泡劑的步驟：在進行第2聚合步驟而製造聚苯乙 烯系樹脂粒子之後、或在聚苯乙烯系樹脂粒子之成長中 途，含浸發泡劑。 在本發明之製造方法中，聚苯乙烯系樹脂種粒子（以 下，簡稱為種粒子）之材料的聚苯乙烯系樹脂，可舉例如苯 乙烯或苯乙烯之衍生物之單獨聚合物。此處，苯乙稀衍生 物可舉例如甲基苯乙烯、對甲基苯乙烯、第三丁基苯乙 烯、氯苯乙烯等。其他，可舉例如：由丙烯腈、富馬酸二 甲酯、富馬酸乙酯等可與苯乙烯共聚合的單體與苯乙烯所 200938572 . 構成之共聚物；併用二乙烯基苯、烷二醇曱基丙烯酸酯等 . 多官能性單體的前述共聚物；添加適量之橡膠狀物質的樹 脂等。但以苯乙烯成分為50質量％以上之共聚物或苯乙烯 單獨聚合物為佳。此聚苯乙烯系樹脂宜為重量平均分子量 為15萬至40萬之範圍者。又，種粒子係可於一部份或全 部使用聚苯乙烯系樹脂回收品。 更進一步，種粒子之粒徑係可依製作之聚苯乙烯系樹 脂種粒子的平均粒徑等而適當調整，例如製作平均粒徑為 ® 1.0mm之聚苯乙烯系樹脂種粒子時，係宜使用平均粒徑為 0. 4至0. 7mm左右的種粒子。 在本發明之製造方法中，苯乙烯系單體可舉例如苯乙 烯或苯乙烯衍生物。此處，苯乙稀衍生物可舉例如α-甲基 苯乙烯、對曱基苯乙烯、第三丁基苯乙烯、氣苯乙烯等。 在本發明中，此等苯乙烯系單體中，亦宜為苯乙烯。 在本發明之製造方法中，丙烯酸酯系單體可舉例如丙 @ 烯酸曱酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸丁酯、丙烯 酸戊酯、丙烯酸己酯等，宜為丙烯酸乙酯、丙烯酸丙酯、 丙烯酸丁酯。 本發明之第1聚合步驟所使用之苯乙烯系單體，係相 對於聚苯乙烯系樹脂種粒子100質量份，為7. 0至80. 0質 量份。當未連7. 0質量份時，成形時之耐熱性降低，若超 過80. 0質量份，則低壓成形性差。較佳係8. 0至72. 0質 量份。 又，本發明之第1聚合步驟所使用之丙烯酸酯系單 9 320980 200938572 體，係相對於聚笨乙烯系樹脂種粒子1〇〇質量份，為2. 〇 至12. 0質量份。當未達2. 〇質量份時，低壓成形性差，若、 超過12· G質量份’則耐熱性會降低。較佳係2. G至11 2 質量份。 ' 添加於本發明之發泡性聚苯乙稀系樹脂粒子中的發泡 劑，且為其彿點為聚苯乙烯系樹脂的軟化點以下，且在常 壓下為氣狀或液狀之有機化合物。可使用例如丙烧、正丁 烧 '異丁烧'正戊烧、異魏、新錢、環魏、環戍二 稀:正己烧、石_等烴類；丙酮、甲基乙基酮等酮類；〇 甲醇、乙醇、異丙醇等醇類；二甲基趟、二乙基謎、二丙 基醚、甲基乙基_等低沸點趟化合物；二氧化碳、氮、氨 等無機氣體等。此等發泡劑可只使用一種，又，亦可併用 —種以上。此等之中’較佳之發泡劑係軸為-45至40°c 為㈣、正丁烧、異丁烧、正躲、異戊烧等。 此發泡劑之添加量相對於聚苯乙烯系樹脂種粒子1〇〇質量 份，宜為5至15質量份之範圍。 — 〇 t若欲藉本發明之製造方法而製造發泡性聚苯乙烯系樹 月曰粒子，係於高壓鍋等反應容器内置入水性媒體，使前述 種粒子分散於該水性媒體，於此水性媒體中，在前述（1) 第1聚合步驟中係使苯乙烯系單體與丙烯酸醋系單體連續 ，或斷續地供給’錢，在前述⑵第2聚合步驟中係只使 苯乙缔系單體連續地或斷續地供給，並在聚合起始劑的存 在下於種粒子表面及/或種粒子㈣絲乙烯—丙賴自旨系 ’、ik物及聚苯乙烯系樹脂成長，而製作特定粒徑的聚苯乙 320980 10 200938572 . 烯系樹脂粒子。 - 在前述（1)第1聚合步驟及（2)第2聚合步驟中，種粒 子之使用量少時，無法使原料單體的聚合控制於適當範 圍，而使聚苯乙烯系樹脂極端地高分子量化或產生大量微 粉末狀之聚苯乙烯系樹脂，製造效率降低。又，使用量多 時，一次的生產所得到的量少，生產性差。因而，種粒子 之適當使用量係相對於聚苯乙烯系樹脂全量宜為10至60 質量％的範圍，更宜為15至50質量％之範圍。 ® 在前述（1)第1聚合步驟及（2)第2聚合步驟中可使用 之聚合起始劑，若為以往於苯乙烯系單體之聚合所使用 者，即無特別限定而可使用，可舉例如：過氧化苯甲醯基、 第三丁基過氧化苯曱酸酯、第三丁基過氧化-2-乙基己酸 酯、過氧化月桂基、過氧化第三丁基、第三丁基過氧化三 甲基乙酸酯、第三丁基過氧化異丙基碳酸酯、第三丁基過 氧化乙酸酯、2, 2-第三丁基過氧化丁烷、第三丁基過氧化 φ -3, 3, 5-三曱基己酸酯、二-第三丁基過氧化六氫對酞酸酯 等有機過氧化物；偶氮雙異丁腈、偶氮雙二甲基戊腈等偶 氮化合物等。此等聚合起始劑中，尤宜為用以得到10小時 之半衰期的分解溫度為80至120°C者。此聚合起始劑亦可 單獨使用一種類，又，亦可併用相異之2種以上之聚合起 始劑。 更進一步，為了使前述種粒子及單體的小滴分散於前 述水性媒體中所使用之懸濁安定劑，若為以往於聚苯乙烯 系樹脂之懸濁聚合所使用者，並無特別限定而可使用，可 11 320980 200938572 舉例如：聚乙烯醇、曱基纖維素、聚丙烯醯胺、聚乙烯基 吡咯烷酮等水溶性高分子；第三磷酸鈣、焦磷酸鎂等難溶 性無機化合物等。此懸濁安定劑亦可單獨使用一種類，又， 亦可混合使用2種以上之懸濁安定劑。 使用難溶性無機化合物作為前述懸濁安定劑時係宜併 用陰離子界面活性劑。如此之陰離子界面活性劑可舉例 如：脂肪酸皂、N-醯基胺基酸或其鹽、烷基醚羧酸鹽等羧 酸鹽；烷基苯磺酸鹽、烷基萘磺酸鹽、二烷基磺酸基琥珀 酸酯鹽、烷基磺酸基乙酸鹽、α-烯烴磺酸鹽等磺酸鹽；高 級醇硫酸酯鹽、第二級高級醇硫酸酯鹽、烷基醚硫酸鹽、 聚氧伸乙基烷基苯基醚硫酸鹽等硫酸酯鹽；烷基醚磷酸酯 鹽、烷基磷酸酯鹽等磷酸酯鹽等。此等陰離子界面活性劑 係可1種單獨使用，或混合2種類以上而使用。 在前述（1)第1聚合步驟中，供給至水性媒體中之苯乙 烯系單體與丙烯酸酯系單體之量係相對於種粒子100質量 份，苯乙烯系單體為7.0至80.0質量份之範圍，又，丙烯 酸酯系單體為2. 0至12. 0質量份之範圍。若（1)第1聚合 步驟中之苯乙烯系單體與丙烯酸酯系單體之量為在前述範 圍内，則可提供一種發泡性聚苯乙烯系樹脂粒子，其於成 形時所使用之水蒸氣的壓力即使為低壓，亦可得到外觀美 麗且具有高強度之發泡成形體，由於可低壓成形，故在成 形步驟中，可縮短每一發射之成形時間。 前述（2)第2聚合步驟係在前述（1)第1聚合步驟結束 後，於高壓鍋等反應容器内的水性媒體中只加入苯乙烯系 12 .320980 200938572 * 單體’在藉前述（1)第1聚合步驟而成長之種粒子上使聚苯 • 乙稀糸樹脂成長’形成聚苯乙稀糸樹脂粒子。於此（2)第2 聚合步驟中使用之苯乙晞系單體的量係無特別限定，但相 對於第2聚合步驟後所得到之聚本乙婦系樹脂粒子的樹脂 成分100質量份宜為30. 0至80.0質量份之範圍。 在本發明之製造方法中’若欲使發泡劑含浸於聚苯乙 烯系樹脂粒子，則可使用以下任一種方法： (a )在製造聚本乙稀系樹脂粒子之後’含浸發泡劑之方法 ❹ （b)或在聚苯乙婦系樹脂粒子之成長中途，含浸發泡劑之方 法。 發泡劑含浸後’取出所製造之樹脂粒子，進行洗淨、 乾燥’得到發泡性聚苯乙烯系樹脂粒子。 本發明之發泡性聚苯乙烯系樹脂粒子係除了前述發泡 劑以外’於聚苯乙烯系樹脂粒子中，亦可依需要而添加一 般使用於發泡性聚苯乙烯系樹脂粒子之製造中之其他的添 ❹加劑，例如氣泡調整劑、可塑劑、溶劑、難燃劑、染料等， 著色劑等。 在本發明之發泡性聚苯乙烯系樹脂粒子之表面，係如 同對於習知之發泡性聚苯乙烯系掛脂粒子一般所實施般， 可塗佈脂肪酸金屬鹽、脂肪酸酯、抗靜電劑等表面處理劑， 藉由進行表面處理劑之塗佈’亦可改善樹脂粒子（珠粒）的 流動性、預備發泡特性等。 然後，說明有關本發明之發泡性聚苯乙烯系樹脂粒子。 本發明之發泡性聚笨乙烯系樹脂粒子含有苯乙烯系單 320980 13 200938572 體與丙烯酸酯系單體之共聚物，其特徵在於： 在藉ATR法紅外線分光分析以分析發泡性聚苯乙烯系 樹脂粒子之表面所得到之紅外線吸收光譜中，求出在 1730cm 1之吸光度D1730與1600CHT1之吸光度D1600後，從 D1730/D1600所算出之吸光度比（A);與 在藉ATR法紅外線分光分析以分析發泡性聚苯乙烯系 樹脂粒子之中心部所得到之紅外線吸收光讀中，求出在 1730cm—1之吸光度D1730與1600CHT1之吸光度D1600後，從 D1730/D1600所算出之吸光度比（B); 係滿足（A)<(B)，且（A)為0· 05以上之關係。 所謂「ATR法紅外線分光分析」係指藉由利用全反射 吸收之一次反射型ATR法以測定紅外線吸收光譜之分析方 法。 此分析方法係使具有高的折射率之ATR稜鏡密接於試 料，通過ATR棱鏡而對試料照射紅外線，將從ATR稜鏡之 射出光進行分光分析之方法。ATR法紅外線分光分析係因 僅使試料與ATR稜鏡密接俾可測定光譜之簡單性、且可進 行深至數#111之表面分析等理由，而廣泛利用於以高分子 材料等有機物為首之各種物質的表面分析。 在本發明中係藉ATR法紅外線分光分析而分析發泡性 聚苯乙稀系樹脂粒子之表面與中心部，在所得到之紅外線 吸收光譜中，求出lMOcnT1之吸光度D1730與1600CHT1之 吸光度D1600。繼而’從前述各吸光度之值，算出樹脂粒 子之表面的吸光度比（A)、與粒子粒子之中心部的吸光度比 320980 200938572 ， ⑻。 * 又’從紅外線吸收光譜所付到之160OcnT1之吸光度 D1600’係指源自於聚苯乙婦系樹脂所含有之苯環的面内振 動之於16OOcnf1附近所出現的譜峰的高度。 又’從紅外線吸收光譜所得到之1730cm—1之吸光度 D1730，係指源自於丙烯酸酯所含有之酯基的c=〇間之伸縮 振動之於1730cm_1附近所出現的譜峰的高度。 又’表面之吸光度係如第1圖所示，為對於發泡性聚 ® 本乙稀糸樹脂粒子1之表面A以ATR法紅外線分光分析進 行測定而求出之值，又，中心部之吸光度係如第2圖所示， 將通過發泡性聚苯乙烯系樹脂粒子丨之中心而切割之截面 的中心部B以ATR法紅外線分光分析進行測定而求出之值。 本發明之發泡性聚苯乙烯系樹脂粒子之如前述般所算 出之樹脂粒子表面的吸光度比（A)、與粒子粒子之中心部的 吸光度比（B)係滿足（A)<(B)且（A)為〇. 〇5以上之關係。 ❹夕亩Hi本發明之發泡性聚苯乙烯系樹脂粒子係在粒子 ^ °所含有之笨乙烯-丙烯酸酯系共聚物成分的比 辰度向，在表層侧有成為低濃度之傾向。又， 之表層部中，亦存在有某程乙酸 酯系共聚物成分。 ^ —發月之發泡性聚苯乙烯系樹脂粒子係由於具有如前 本烯丙烯酸酯系共聚物成分之分布構造，故於成形 時所吏之水条氣的堡力即使為低壓，亦可得别外觀美麗 強度之發泡成形體，又，即使在以高的蒸氣壓力 15 320980 200938572 成形時，亦可得到不易因耐熱性降低而造成成形體外觀劣 „ 化之發泡成形體。當不滿足（A)<(B)且（A)為0. 05以上之關 . 係時，很難得到前述之效果。 前述吸光度比（A)宜為0. 05至0. 50之範圍内，更宜為 0. 08至0. 47的範圍。 前述吸光度比（B)宜為0. 20至0. 60之範圍内，更宜為 0. 23至0. 55的範圍。 更進一步，前述吸光度比（A)與（B)之比（B/A)為1.10 至3. 00的範圍内，更宜為1.17至2. 88的範圍内。 ❹ 本發明之發泡性聚苯乙烯系樹脂粒子係可藉由前述之 本發明的製造方法而有效率地製造，但製造方法不限定於 此。 本發明之發泡性聚苯乙烯系樹脂粒子係以體密度成為 0. 01至0. 033g/cm3的範圍之方式進行預備發泡而形成預備 發泡粒子，更進一步使此預備發泡粒子填充於成形模之模 穴内，予以加熱並進行模内發泡成形，俾可使用於製造發 八 〇 泡成形體。 [實施例] 以下，依實施例而表示本發明之具體例，但以下之實 施例僅為本發明之例示，本發明不只限定於以下之實施 例。又，在以下之實施例、比較例中，發泡性聚苯乙烯系 樹脂粒子之吸光度比的結果係與發泡劑含浸前之聚苯乙烯 系樹脂吸光度比的結果相同。 實施例1 16 320980 200938572 (種粒子之製造） 於内容量1GG公升之附有搜拌機的聚合容器中，供給 水40000g、作為懸濁安定劑之第三鱗㈣l〇〇g及作為陰 離子界面活性劑之十二烧基苯續酸㉝2.⑽，—邊攪摔，一 邊添加苯乙烯4〇_g、作為聚合起始劑之魏化苯甲酸基 96.0g及第三丁基過氧化笨甲_旨⑽後，再昇溫至90 C而聚合。繼而’以此溫度保持6小時，更進一步，昇溫 至125 C後保持2小8^ ’其後進行冷卻而得到聚苯乙 榭脂(Ά。 _分前述聚苯乙烯系樹脂粒子⑷，得到作為種粒子之 粒徑0.5至0.71咖範圍的聚笨乙婦系樹脂粒子⑹。 其次，於内容量5公升之附有搜摔機的聚合容器内， 供給水2GG0g、前述聚笨乙埽系樹脂粒子⑹、作為懸 濁安定劑之焦碟酸鎮6. 0§及作為陰離子界面活性劑之十 4基苯賴紅Gg，-錢拌，—邊昇溫至肌。 ❿（第1聚合步驟） :然後’使作為聚合起始劑之過氧化苯甲釀基㈣及第 丁基過氧化苯m 1.5g溶解於苯⑽對於種 質量份為36質量份)、丙稀酸丁 質量份為6質量份）之混合液中，將其供給至前述 =升之聚合容器中，以75t保持6q分鐘。 (第2聚合步驟） 於經過60分鐘後，使反應 同時並使用泵將苯乙烯】29〇g 液以150分鐘昇溫至11(TC， 以150分鐘逐次定量地供給 320980 17 200938572 聚S谷器内，其後昇溫至120。(：，在經過2小時後進行 》 冷卻而得到聚苯乙烯系樹脂粒子（c)。 (樹脂粒子之吸光度比） 對於所得到之聚苯乙烯系樹脂粒子（c)，依下述〈吸光 ^比之測定〉而測定樹脂粒子的表面之吸光度比（A)與中心 崢之吸光度比（B)。其結果表示於表1中。 又，算出吸光度比（A)與（B)之比（（B)/(A))，此亦表示 於表1中。 又’對於所得到之發泡性聚笨乙烯系樹脂，亦依下述< ❹ 吸光度比之測定〉而測定吸光度比。 (吸光度比之測定） 吸光度比（D17 3 0 / D16 0 0 )係以下述之要領測定。 亦即’對於隨意選擇之1〇個各樹脂粒子的表面（第1 圖中之付號A)、及通過粒子中心而切割之截面之中心部（圖 2中之付號B)，藉ATR法紅外線分光分析進行粒子表面分 軒而得到紅外線吸收光譜。分別從各红外線吸收光譜算出 ❹ °及光度比（D1730/D1600)，將對於表面a算出之吸光度比的 相加平均作為吸光度比（A)，並將對於中心部b算出之吸光 度比的相加平均作為吸光度比（B)。 吸光度D1730及D1600係例如使用從Nicolet公司以 商品名「富利葉變換紅外分光光度計MAGMA 560」所販賣 之測定裝置而測定。 又，從紅外線吸收光譜所得到之1600cm—1之吸光度 Μ 600係指源自於聚苯乙烯系樹脂所含有之苯環的面内振 18 320980 200938572 » 動之於】600CBT1附进戶斤山 斤出現的譜峰的高度。 • 又，從紅外線吸收决抑 D1730係指源自於丙烯酸^所传到之]73〇cm ]之吸光度 振動之於麗^ W⑶基的⑽間之伸縮 迎所出現的譜峰的高度。 (發泡劑含浸） 繼而，於另一個曰Pie _ 中，供-水22〇〇S、：升之附有攪拌機的聚合容器 ο 聚本乙烯系樹脂粒子（c) 18〇〇g、作為 1安定劑之㈣_心及十二 乍為 一邊攪拌，一邊昇溫至7nv甘A ^ i·0轻， C。其-人’將作為發泡助添丨 己烷27.0g及作為可j ^ 之環 塑劑之己二酸二異丁酯12. 6g置人於 I合容器内而密閉，昇㈤ 置入於 ^ 歼/皿至i〇oc。其次，將作為發洎劊 之正丁烷90g壓入已荖士叙奸β / θίχ/包劑 人六。。 匕置有聚苯乙烯糸樹脂種粒子（c)之聚 口 益内而保持 3，j、n* AL· . r\ λ ο 時後’冷钟至3〇 C以下之後從聚合穷 器内取出，乾焯之棘 ^ ° ^ 發泡性聚苯乙稀系樹月旨粒子。 而的 實施例2 _除了在第1聚合步驟中，使作為聚合起始劑之過氧化 本曱醯基6. 8g及第三丁基過氧化苯曱酸g| h 5g溶解於 乙烯200g(相對於種板子1〇〇質量份為4〇質量份）、丙 ^醋1Gg(相對於種⑽_質量份為2質量份）的混合 乂以外，其餘係與實施例i同樣做法而得到發泡 乙烯系樹脂粒子。 與實施例1同樣地，對於發泡劑含浸前之聚苯乙稀 树脂粒子（C )測定矣；g； , ζ、 彡j疋表面之吸光度比（Α)與中心部之吸光度比 .320980 19 200938572 結果表示於表1中。 ⑻，又’算出此等之比(⑻/(A))。 實施例3 ^ 1〇^〇 稀酸丁酯56加_粒子則量份為ll 2 f量份)的 ^二，其餘係與實施例1同樣做法而得到發泡性 聚本乙烯系樹脂粒子。 與實施例1同樣地，對於發泡劑含浸前之聚苯乙婦系〇 樹脂粒子（c)測定表面之吸光度比（A)與中心部之吸光度比 (B)，又，算出此等之比（（B)/(A))。結果表示於表丨^。 實施例4 除了在第1聚合步驟中，使作為聚合起始劑之過氧化 苯甲醯基6. 8g及第三丁基過氧化苯甲酸酯15运溶解於苯 乙烯40g(相對於種粒子1〇〇質量份為8質量份）、丙烯酸 丁酯30g(相對於種粒子1〇〇質量份為6質量份）的混合液 ❹ 中；以及在第2聚合步驟中，以15〇分鐘昇溫，並將以泵逐 次定量供給至聚合容器内之苯乙烯設為143〇g以外，其餘 係與實施例1同樣做法而得到發泡性聚苯乙烯系樹脂粒 子。 與實施例1同樣地’對於發泡劑含浸前之聚苯乙婦系 樹脂粒子（c )測定表面之吸光度比（A )與中心部之吸光度比 (B) ’又’算出此等之比（（B)/(A))。結果表示於表1中。 實施例5 20 320980 200938572 , 除了在第1聚合步驟中，使作為聚合起始劑之過氧化 > 苯甲醯基6. 8g及第三丁基過氧化苯甲酸酯1. 5g溶解於苯 乙烯360g(相對於種粒子100質量份為72質量份）、丙稀 酸丁酯30g(相對於種粒子100質量份為6質量份）的混合 液中；以及在第2聚合步驟中，以150分鐘昇沒，並將以果 逐次定量供給至聚合容器内之苯乙烯設為lll0g以外，其 餘係與實施例1同樣做法而得到發泡性聚苯乙歸系樹脂粒 子。 ® 與實施例1同樣地，對於發泡劑含浸前之聚苯乙稀系 樹脂粒子（C)測定表面之吸光度比（A)與中心部之吸光度比 (B) ’又，算出此等之比（（B)/(A))。結果表示於表i中。 實施例6 除了在第1聚合步驟中，將所使用之丙烯酸酯種類設 為丙烯酸乙酯，使作為聚合起始劑之過氧化笨甲醯基6 % 及第三丁基過氧化苯曱酸酯Ug溶解於苯乙烯i7〇g(相對 ❹於種粒子100質量份為34質量份）、丙烯酸乙· 4〇g(相對 於種粒子100質量份為8質量份）的混合液中，以15〇分鐘 昇溫，並將以泵逐次定量供給至聚合容器内之笨乙烯系單 體設為1290g以外，其餘係與實施例】同樣做法而得: 泡性聚苯乙烯系樹脂粒子。 私 與實施例1同樣地，對於發泡劑含浸前之聚苯乙烯系 樹月曰粒子（c)測定表面之吸光度比（A)與中心部之吸光度= (B)，又，算出此等之比（（B)/(A))。結果表示於表^ 。 實施例7 320980 21 200938572 一除了使作為聚合起始劑之過氧化笨曱醯基6 8g及第 一丁基過氧化苯甲酸酯15g溶解於笨乙烯系單體18〇运、 丙烯酸丁酉曰30g的混合液中，以15〇分鐘昇溫並將以泵 逐-人足量供給至聚合容器内之苯乙烯系單體設為75〇g以 外其餘係與實施例1同樣做法而得到發泡性聚苯乙烯系 樹脂粒子。 與實施例1同樣地，對於發泡劑含浸前之聚苯乙烯系 樹脂粒子（C)測定表面之吸光度比（A)與中心部之吸光度比 (B) ’又，算出此等之比（（B)/(A))。結果表示於表1中。❹ 實施例8 除了使作為聚合起始劑之過氧化苯曱醯基6. 8g及第 二丁基過氧化笨曱酸酯1· 5g溶解於苯乙烯系單體18〇g、 丙烯酸丁酯30g的混合液中，以15〇分鐘昇温，並將以泵 逐次定量供給至聚合容器内之苯乙烯系單體設為2〇〇〇g以 外，其餘係與實施例1同樣做法而得到發泡性聚苯乙烯系 樹脂粒子。 與實施例1同樣地，對於發泡劑含浸前之聚苯乙烯系 樹脂粒子（c)測定表面之吸光度比（Α)與中心部之吸光度比 (Β) ’又’算出此等之比（（Β)/(Α))。結果表示於表1中。 實施例9 除了使作為聚合起始劑之過氧化苯甲醯基6. 8g及第 三丁基過氧化笨甲酸酯1.5g溶解於苯乙烯系單體i80g、 丙烯酸丁酯30g的混合液中，以15〇分鐘昇温，並將以泵 逐次定量供給至聚合容器内之苯乙烯系單體設為5〇〇g以 22 320980 200938572 同樣做法而得到發泡性聚苯乙烯系 外’其餘係與實施你】 樹脂粒子。 :二1同樣地’對於發泡劑含浸前之聚苯乙烯系 :粒又子(=定表面之吸光度比⑷與中心部之吸光度比 ’又’异出此等之比（（b)/(a))。結果表 實施例ίο τ 除了使作為聚合起始劑之過氧化苯甲醯基6· 8g及第 三丁基過氧化苯甲酸酯1.¾溶解於苯乙烯系單體18〇g、 ® 丙烯酸丁酯30g的混合液中，以150分鐘昇溫，並將以泵 逐次定量地供給至聚合容器内之苯乙烯系單體設為275〇g 以外’其餘係與實施例1同樣做法而得到發泡性聚苯乙烯 系樹脂粒子。 與實施例1同樣地’對於發泡劑含浸前之聚苯乙稀系 樹脂粒子（c)測定表面之吸光度比(A)與中心部之吸光度比 (B)，又，异出此等之比（（b)/(A))。結果表示於表1中。 φ 比較例1 於實施例1中’除了在第1聚合步驟不使用丙稀酸酯， 並將過氧化笨甲醯基6· 8g及第三丁基過氧化笨甲酸醋 1.5g設為苯乙烯210g(相對於種粒子1〇〇質量份為犯質量 伤）以外，其餘係與實施例1同樣做法而得到發泡性聚苯乙 細系樹脂粒子。 與實施例1同樣地，對於發泡劑含浸前之聚苯乙婦系 樹脂粒子（C )測定表面之吸光度比（A )與中心部之吸光度比 (B)，又，算出此等之比（（b)/(a))。結果表示於表i中。 320980 23 200938572 比較例2 —除了在第1聚合步驟中，使作為聚合起始劑之過氧化 本甲基6.8g及第三丁基過氧化苯曱酸醋1.5g溶解於笨 乙烯202g(相對於種粒子1〇〇質量份為4〇 .4質量份）、丙 :酸丁醋8g(相對於種粒子100質量份為1.6質量份)的混 液中’以及在第2聚合步驟中，以150分鐘昇溫，並將以 栗逐次定量供給至聚合容器内之笨乙烯設為1290質量份 /外’其餘係與實施例1同樣做法而得到發泡性聚苯乙烯 系衔脂粒子。 貫施例1同樣地，對於發泡劑含浸前之聚笨乙埽系 子月曰粒子（c)洌定表面之吸光度比（a)與中心部之吸光度比 (B) ’又’算出此等之比（（B)/(A))。結果表示於表1中。 比軼例3 ^ 除了在第1聚合步驟中，使作為聚合起始劑之過氧化 笨甲醯基6· 8g及第三丁基過氧化苯曱酸酯i.5g溶解於笨 己歸140g(相對於種粒子1〇〇質量份為28質量份）、兩缚 駿丁酯70g(相對於種粒子1〇〇質量份為14質量份）的混合 〇 峡中；以及在第2聚合步驟中，以150分鐘昇溫，並將以粟 I次定量供給至聚合容器内之苯乙烯設為1290g以外，其 餘係與實施例1同樣做法而得到發泡性聚苯乙烯系樹脂粒 子。 與實施例1同樣地，對於發泡劑含浸前之聚苯乙埽系 樹脂粒子（c)測定表面之吸光度比（A)與中心部之吸光度比 (δ) ’又，算出此等之比（（B)/(A))。結果表示於表1中。 24 320980 200938572 „ 比較例4 除了在第 1 ..»β Ο 聚合步驟中，使作為聚合起始劑之過氧化 本甲醯基6. 8g及楚_ 7私on ^ 军三丁基過氧化苯甲酸醋1.5g溶解於笨 乙烯30g(相對於强 + ___ Qn 、種粒子100質量份為6質量份）、丙烯酸 丁酯30g(相對於潴 , ^ ^ 、種叔子1〇〇質量份為6質量份）的混合液 T ;以及在第2 5只八μ k s步驟中，以150分鐘昇溫，並將以泵逐 人疋量供至聚合容器内之苯乙烯設為1440質量份以 〇 外，其餘係與實祢彳5, , ^ 、 例1同樣做法而得到發泡性聚苯乙婦系 樹‘脂粒子。 與實施例1同姆_iL .,. J樣地，對於發泡劑含浸前之聚苯乙缚系 樹月曰粒子（e ) /収表面之吸光纽（a )與巾^部之吸光度比 (B)，又’算出此等之比((B)/(A))。結果表示於表i中。 比較例5 ^除了在第1聚合步驟中，使作為聚合起始劑之過氧化 苯甲醯基6· 8g及第三丁基過氧化苯甲酸醋1. 5g溶解於苯 ®乙締460g(相對於種粒子100質量份為92質量份）、丙烯 酸丁酯30g(相對於種粒子100質量份為6質量份）的混合 液中；以及在第2聚合步驟中，以150分鐘昇溫，並將以泵 逐次定量供給至聚合容器内之苯乙烯設為1010質量份.以 外’其餘係與實施例1同樣做法而得到發泡性聚苯乙稀系 樹脂粒子。 與實施例1同樣地，對於發泡劑含浸前之聚苯乙稀系 樹脂粒子（c)測定表面之吸光度比（A)與中心部之吸光度比 (B) ’又，算出此等之比（（b)/(a))。結果表示於表1中。 25 320980 200938572 比較例6 於内容量5公升之附有攪拌機的聚合容器中，供給水 . 2000質量份、前述聚苯乙烯系樹脂粒子（B)500質量份、作 為懸濁安定劑之焦磷酸鎂6.0質量份及作為陰離子界面活 性劑之十二烧基苯確酸妈0. 3質量份，一邊擾拌，一邊昇 溫至75°C。 然後，預先製成苯乙烯1470質量份與丙烯酸丁酯30 質量份之混合液，使用該混合液210質量份（相對於種粒子 100質量份，苯乙烯為41. 2質量份、丙烯酸丁酯為0. 84 ❹ 質量份）溶解過氧化苯曱醯基6.8質量份及第三丁基過氧 化笨曱酸酯1. 5質量份，在供給至前述5公升之聚合容器 後，以75°C保持60分鐘。 經過60分鐘後，使反應液以150分鐘昇温至110°C， 同時並使用泵將前述苯乙烯系單體與丙烯酸丁酯之混合液 1290質量份以150分鐘逐次定量地供給至聚合容器内後， 昇溫至120°C，經過2小時後冷卻，得到苯乙烯系樹脂粒 q 子（c)。其後係與實施例1同樣做法而得到發泡性聚苯乙烯 系樹脂粒子。 與實施例1同樣地，對於發泡劑含浸前之聚苯乙烯系 樹脂粒子（c)測定表面之吸光度比（A)與中心部之吸光度比 (B)，又，算出此等之比（（B)/(A))。結果表示於表1中。 26 320980 200938572 .[表 1]200938572 VI. TECHNOLOGICAL FIELD OF THE INVENTION The present invention relates to a method for recording a polyphenylene-based tree __ : The invention relates to a method for producing a foamable polystyrene-based resin particle, which is used in the forming of a >a佴亍旳1, and has a beautiful appearance and a pressure of two gas, even if The low pressure can also be formed, so in the forming step, the foamed molded body can be formed at a low pressure according to the forming time of each of the short shots according to 2_year 77. Priority No. 2008-19000 is preferred in Japan. [Prior Art] Auxiliary Glue: A foamed plastic enamel resin foam molded body used for containers, bales, and cushioning materials. The system of the bismuth-based acetylene-based resin: a polystyrene-based resin foamed by a styrene-based resin, which has a foaming property such as a volatile foaming agent, such as a foaming polystyrene: 曰θ瘵 gas, etc. The heat medium is heated and foamed (pre-foamed) until the desired bulk product is filled with the U* shellfish particles, and after the composition of the second a-), the mold of the preliminary foam forming mold is = : The shape of the cavity (the one-track medium is used to prepare the foamed particles by vapor or the like: the body is heated to form the foamed molded body. The polystyrene resin obtained by the sputum broadcast The density of the foamed body is almost the same as that of A, and the body density is set according to the strength required by the polystyrene 320980 200938572 olefin resin foam molded body and the expandable polystyrene resin particles. 017至0. 017g/cm3 The polystyrene-based resin foam molded body is used in a food container such as a packaging material such as a home appliance, or a fish container, and the like. The density is supplied to the market. In this forming step, the appearance or strength of the foamed molded body is When the temperature of the heating medium such as gas (when it is water vapor, it is the heating vapor pressure), for example, when heating with steam, if the heating pressure is increased, the appearance or strength of the molded body tends to increase, but Further, if the heating pressure is high, the surface of the foamed molded body is melted by heat, resulting in deterioration of the appearance of the foamed molded body. Conversely, if the heating pressure is lowered, the heating time is lowered. In the molding, the molding time per shot is shortened, but the subsequent foaming particles are weakened, and the appearance and strength of the foam molded body are deteriorated. Thus, the vapor pressure of the vapor in the forming step is from a low pressure to The high pressure can be formed to some extent freely, and is one of the important characteristics of the expandable polystyrene resin particles ◎. In general, in the production of a polystyrene resin foam molded body, the molding time of each emission In relation to the strength of the foamed molded body, when the forming time is long, a foamed molded body having high strength can be obtained, and when the forming time is short, foaming can be seen. The strength of the shape is reduced. The conventional technique for shortening the molding time of the polystyrene-based resin foam molded body is, for example, Patent Documents 1 to 5. Patent Document 1 proposes a foaming polymerization. Styrene Resin 4 320980 200938572 The surface of the particles is coated with a solid at room temperature and is a 6-mesh reticular aliphatic pro-ester (4) method. The powder time under X greatly shortens the cooling time, while in the forming time = It can be used in forming, but it has a tendency to decrease with strength. (5) Knowing that there is a lot of liquid in the center of the patent document 2, specializing in the application of mobile stone ants, patent documents in the literature 3, patent reading " mention ❹ ❹ The method of the surface of the eucalyptus silk newcomer. 1) Ethylene cannot be reduced as the strength of the foamed molded body. The method of 4 is also [Technical Literature] [Patent Literature] [Patent Document 1] [Patent [Patent Document 3] [Patent Document 3] [Patent Document 5] [Patent Document 5] [Invention] Japanese Patent Publication No. Sho 58-56568 (Japanese Unexamined Patent Publication No. Hei No. Hei. Kai Zhao 52165 Japanese Patent Publication No. 59-202235 [Problem to be Solved by the Invention] The pressure γ of the water vapor used at the time of molding can also obtain a foam molded body having a beautiful appearance and high strength. It can be formed at a low pressure, so that the forming time per one shot can be shortened in the forming step. [Means for Solving the Problem] 320980 200938572 In order to achieve the above object, the present invention provides a method for producing expandable polystyrene resin particles, which is obtained by the following steps to obtain expandable polystyrene resin particles: 0至80. 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 The mass fraction and the acrylate monomer are 2.0 to 12.0 parts by mass, so that the seed particles absorb the monomers, and polymerize to grow the polystyrene resin particles; (2) the second polymerization step: then And supplying only the styrene monomer to the dispersion, allowing the seed particles to absorb the monomer, and polymerizing to grow the polystyrene resin seed particles; and (3) the step of impregnating the foaming agent: performing the second step After the polystyrene resin particles are produced in the polymerization step or during the growth of the polystyrene resin particles, the foaming agent is impregnated. Moreover, the present invention provides a foamable polystyrene resin particle containing a copolymer of a styrene monomer and an acrylate monomer, which is characterized in that it is analyzed by ATR infrared spectroscopy to analyze the future. In the infrared absorption spectrum obtained on the surface of the foamable polystyrene resin particles, the absorbance ratio (A) calculated from D1730/D1600 after the absorbance D1630 of 1730 CHT1 and the absorbance D1600 of 1600 CHT1 were determined; Infrared spectroscopic analysis, in the infrared absorption spectrum obtained by analyzing the central portion of the foamable polystyrene resin particles, the absorbance D1730 at 1730 CHT1 and the absorbance D1600 at 1600 cm 1 were determined, 6 320980 200938572. Calculated from D1730/D1600 Absorbance. Satisfaction (A) <(B), and (A) is a relationship of 0·〇5 or more. In the foamable polystyrene-based dendritic particles, the absorbance ratio is preferably in the range of 0.05 to 0.50, and the absorbance ratio (B) is preferably in the range of 〇 to 0·60. The foaming polystyrene-based tree-shaped particles, the ratio of the absorbance to the (B) ratio (B/A) is preferably in the range of 1.10 to 3.0 。. It is preferable to obtain the foaming 11 polystyrene resin particle manufacturing method. The present invention provides a kind of preliminary foaming particle which is a body of a front foaming polystyrene resin particle. The density is 〇. 〇 〇 VM VM VM VM VM VM VM VM VM VM VM VM VM VM VM VM VM VM VM VM VM VM VM VM VM VM VM VM VM VM VM VM VM VM VM VM VM VM VM VM VM VM VM VM VM VM VM The result of the bubble forming by heating the dragon. ^ ❹ [Effect of the invention] The foamable polystyrene-based sap of the present invention can be made into a water vapor at the time of molding. A foamed molded body that has a beautiful view and has a strong strength. It is clear that /p can be foamed into Even when it is formed by the treatment of the therapeutic milk S, it is not easy to deteriorate due to the appearance of the low-profile molded body. It is possible to provide a foamed molded body κ. The conditions for forming the yam are very wide, and it is desirable for various moldings. 320980 7 200938572 The foamable polystyrene resin particles and the preliminary foamed particles of the present invention have less change in foaming performance over time than conventional products, and have a long history of storage, which is comparable to conventional products. Further, the foaming property of the expandable polystyrene resin particles of the present invention is obtained by the following steps to obtain expandable polystyrene resin particles: (1) 0质量份。 0 mass parts of the styrene monomer is supplied to the styrene monomer. And 2.0 parts by mass of the acrylate monomer, the seed particles are absorbed by the seed particles, and polymerized to grow the polystyrene resin seed particles; (2) the second polymerization step: then, In the dispersion Supplying a styrene monomer, absorbing the monomer by the seed particles, and polymerizing to grow the polystyrene resin seed particles; and (3) a step of impregnating the foaming agent: producing the polystyrene in the second polymerization step In the method of the present invention, the polystyrene resin seed particles (hereinafter, simply referred to as seed particles) are polyphenylene. The vinyl resin may, for example, be a single polymer of a derivative of styrene or styrene. Here, examples of the styrene derivative include methyl styrene, p-methyl styrene, t-butyl styrene, and chlorine. Styrene, etc. Other examples include a copolymer of a monomer copolymerizable with styrene such as acrylonitrile, dimethyl fumarate or ethyl fumarate and styrene 200938572. A phenyl group, an alkanediol methacrylate or the like. The above copolymer of a polyfunctional monomer; a resin to which an appropriate amount of a rubbery substance is added, or the like. However, a copolymer having a styrene component of 50% by mass or more or a styrene alone polymer is preferred. The polystyrene resin is preferably in the range of from 150,000 to 400,000 by weight average molecular weight. Further, the seed particles may be used in part or in all of the polystyrene resin recycled product. Further, the particle diameter of the seed particles can be appropriately adjusted depending on the average particle diameter of the produced polystyrene resin seed particles, and the like, for example, when a polystyrene resin particle having an average particle diameter of 1.0 mm is produced, The seed particles having an average particle diameter of about 0.4 to about 0.7 mm. In the production method of the present invention, the styrene monomer may, for example, be styrene or a styrene derivative. Here, examples of the styrene derivative include α-methylstyrene, p-nonylstyrene, t-butylstyrene, and gas styrene. In the present invention, among these styrene monomers, styrene is also preferred. In the production method of the present invention, the acrylate monomer may, for example, be decyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate or hexyl acrylate, and is preferably ethyl acrylate. Propyl acrylate, butyl acrylate. 0至80. 0质量份。 The styrene monomer is used in the first step of the present invention. When the amount is not more than 8.0 parts by mass, the heat resistance at the time of molding is lowered, and if it exceeds 80. 0 parts by mass, the low-pressure moldability is inferior.至质量质量份。 Preferably 0. 0 to 72.0 mass parts. 0质量至1. 0质量份。 The acrylate-based single-layer 9 320980 200938572, the amount of the styrene-based resin particles of the present invention is 2. 〇 to 12. 0 parts by mass. When the amount is not more than 2.5% by mass, the low-pressure moldability is inferior, and if it exceeds 12 g of the mass part, the heat resistance is lowered. Preferably it is from 2. G to 11 2 parts by mass. The foaming agent added to the foamable polystyrene-based resin particles of the present invention is a softening point or lower of the polystyrene-based resin, and is gas or liquid at normal pressure. Organic compound. For example, it is possible to use, for example, a propylene, a butyl ketone, a butyl ketone, a butyl ketone, a ketone, a ketone, a ketone, a ketone, a ketone, a ketone, a ketone, a ketone, and the like. Classes; alcohols such as methanol, ethanol, and isopropanol; low-boiling ruthenium compounds such as dimethyl hydrazine, diethyl mystery, dipropyl ether, and methyl ethyl ketone; inorganic gases such as carbon dioxide, nitrogen, and ammonia. These blowing agents may be used alone or in combination of more than one. Among these, the preferred foaming agent has an axis of -45 to 40 °c of (four), n-butyl, isobutyl, ortho-, iso-pentane and the like. The amount of the foaming agent to be added is preferably in the range of 5 to 15 parts by mass based on 1 part by mass of the polystyrene resin seed particles. — 〇 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 发泡 发泡 发泡 发泡 发泡 发泡 发泡 发泡 发泡 发泡 发泡 发泡 发泡 发泡 发泡 发泡 发泡 发泡 发泡 发泡In the first polymerization step (1), the styrene monomer and the acrylic acid vine monomer are continuously or intermittently supplied with "money", and in the second polymerization step (2), only the phenylethylene system is used. The monomer is continuously or intermittently supplied, and in the presence of a polymerization initiator, the surface of the seed particles and/or the seed particles (4), the vinyl-propylene-based, the ik, and the polystyrene resin are grown. Polystyrene 320980 10 200938572. Alkene resin particles were produced. - In the first polymerization step (1) and the second polymerization step (2), when the amount of the seed particles used is small, the polymerization of the raw material monomers cannot be controlled to an appropriate range, and the polystyrene resin is extremely high. The molecular weight is increased or a large amount of fine powdery polystyrene resin is produced, and the production efficiency is lowered. Further, when the amount of use is large, the amount obtained in one production is small, and the productivity is poor. Therefore, the appropriate amount of the seed particles is preferably in the range of 10 to 60% by mass, and more preferably in the range of 15 to 50% by mass based on the total amount of the polystyrene resin. ® The polymerization initiator which can be used in the above (1) first polymerization step and (2) second polymerization step is not particularly limited as long as it is conventionally used for polymerization of a styrene monomer. For example, benzammonium peroxide, t-butyl peroxybenzoate, t-butylperoxy-2-ethylhexanoate, lauryl peroxide, tributyl peroxide, Tributyl peroxy trimethyl acetate, t-butyl peroxy isopropyl carbonate, t-butyl peroxyacetate, 2, 2-tert-butyl peroxybutane, third An organic peroxide such as oxidized φ -3,3,5-tridecyl hexanoate or di-tert-butylperoxy hexahydrophthalate; azobisisobutyronitrile, azobisdimethyl An azo compound such as valeronitrile or the like. Among these polymerization initiators, those having a decomposition temperature of 80 to 120 ° C for obtaining a half-life of 10 hours are particularly preferable. The polymerization initiator may be used singly or in combination of two or more kinds of polymerization initiators. Further, the suspension stabilizer used for dispersing the droplets of the above-mentioned seed particles and monomers in the aqueous medium is not particularly limited as long as it is a user of suspension polymerization of a polystyrene resin. It can be used, for example, 13 320980 200938572 Examples include: water-soluble polymers such as polyvinyl alcohol, mercapto cellulose, polypropylene decylamine, polyvinylpyrrolidone; poorly soluble inorganic compounds such as calcium phosphate or magnesium pyrophosphate. The suspension stabilizer may be used singly or in combination of two or more kinds of suspension stabilizers. When a poorly soluble inorganic compound is used as the suspension stabilizer, an anionic surfactant is preferably used. Such an anionic surfactant may, for example, be a fatty acid soap, a N-mercaptoamino acid or a salt thereof, a carboxylate such as an alkyl ether carboxylate; an alkylbenzenesulfonate, an alkylnaphthalenesulfonate, or a second a sulfonate such as an alkyl sulfosuccinate salt, an alkyl sulfonate acetate or an α-olefin sulfonate; a higher alcohol sulfate salt, a second-grade higher alcohol sulfate salt, an alkyl ether sulfate, Sulfate salts such as polyoxyethylene ethyl phenyl ether sulfate; phosphate salts such as alkyl ether phosphates and alkyl phosphates. These anionic surfactants can be used singly or in combination of two or more kinds. In the first polymerization step (1), the amount of the styrene monomer and the acrylate monomer supplied to the aqueous medium is 7.0 to 80.0 parts by mass based on 100 parts by mass of the seed particles.范围范围范围内。 The range of the range of 2. 0 to 12. 0 parts by mass. When the amount of the styrene monomer and the acrylate monomer in the first polymerization step is within the above range, a foamable polystyrene resin particle which is used in molding can be provided. Even if the pressure of the water vapor is low pressure, a foamed molded body having a beautiful appearance and high strength can be obtained, and since it can be formed at a low pressure, the molding time for each emission can be shortened in the forming step. In the second (2) second polymerization step, after the end of the first polymerization step (1), only the styrene system is added to the aqueous medium in the reaction vessel such as a pressure cooker. 12.320980 200938572 * The monomer 'by the above (1) The polyphenylene sulfonium resin is grown on the seed particles grown in the first polymerization step to form polystyrene resin particles. The amount of the styrene monomer used in the second polymerization step is not particularly limited, but is preferably 100 parts by mass based on the resin component of the polyethylene resin particles obtained after the second polymerization step. It is in the range of 30.0 to 80.0 parts by mass. In the production method of the present invention, "If the foaming agent is to be impregnated with the polystyrene resin particles, any of the following methods may be used: (a) After impregnating the foaming agent after the production of the polyethylene-based resin particles Method ❹ (b) or a method of impregnating a foaming agent in the middle of the growth of the polystyrene resin particles. After the impregnation agent is impregnated, the resin particles produced are taken out, washed, and dried to obtain expandable polystyrene resin particles. In addition to the above-mentioned foaming agent, the expandable polystyrene resin particles of the present invention may be added to the polystyrene resin particles as needed, and are generally used in the production of expandable polystyrene resin particles. Other additives such as bubble modifiers, plasticizers, solvents, flame retardants, dyes, etc., colorants and the like. The surface of the expandable polystyrene resin particles of the present invention can be coated with a fatty acid metal salt, a fatty acid ester, or an antistatic agent as is conventionally used for the foamable polystyrene resin particles. The surface treatment agent can also improve the fluidity of the resin particles (beads), the preliminary foaming characteristics, and the like by performing the coating of the surface treatment agent. Next, the expandable polystyrene resin particles of the present invention will be described. The expandable polystyrene-based resin particles of the present invention contain a copolymer of a styrene-based single 320980 13 200938572 body and an acrylate-based monomer, which is characterized in that an expandable polystyrene is analyzed by infrared spectroscopic analysis by ATR method. In the infrared absorption spectrum obtained on the surface of the resin particles, the absorbance (D) calculated from D1730/D1600 after the absorbance D1600 of 1730 cm 1 and the absorbance D1600 of 1600 CHT1 were determined, and the infrared spectroscopic analysis by the ATR method was used. In the infrared absorption light reading obtained by analyzing the center portion of the expandable polystyrene resin particles, the absorbance ratio D1630/D1600 calculated at the absorbance D1730 of 1730 cm-1 and the absorbance D1600 of 1600 CHT1 was determined (B). ; is satisfied (A) <(B), and (A) is a relationship of 0.05 or more. The "ATR method infrared spectroscopic analysis" refers to an analysis method for measuring an infrared absorption spectrum by a primary reflection type ATR method using total reflection absorption. In this analysis method, an ATR having a high refractive index is closely attached to a sample, and the sample is irradiated with infrared rays by an ATR prism, and a method of spectroscopic analysis is performed by emitting light from the ATR. ATR-based infrared spectroscopic analysis is widely used in organic materials such as polymer materials because it can be used to measure the simplicity of the spectrum and the surface analysis of #111. Surface analysis of matter. In the present invention, the surface and the center portion of the expandable polystyrene resin particles are analyzed by infrared spectroscopic analysis by ATR method, and the absorbance D1600 of lMOcnT1 and the absorbance D1600 of 1600 CHT1 are obtained in the obtained infrared absorption spectrum. Then, from the values of the respective absorbances, the absorbance ratio (A) of the surface of the resin particles and the absorbance ratio of the center of the particle particles 320980 200938572 (8) were calculated. * The absorbance D1600' of 160OcnT1 from the infrared absorption spectrum refers to the height of the peak appearing in the vicinity of 16OOcnf1 derived from the in-plane vibration of the benzene ring contained in the polystyrene resin. Further, the absorbance D1730 of 1730 cm-1 obtained from the infrared absorption spectrum refers to the height of the peak appearing at around 1730 cm_1 from the c=〇 stretching vibration of the ester group contained in the acrylate. In addition, as shown in Fig. 1, the absorbance of the surface is a value obtained by measuring the surface A of the foamable poly(ethylene) resin particle 1 by ATR infrared spectroscopic analysis, and the absorbance at the center portion. As shown in Fig. 2, the center portion B of the cross section cut by the center of the expandable polystyrene resin particle crucible is measured by ATR infrared spectroscopic analysis. The ratio of the absorbance of the surface of the resin particles (A) calculated on the surface of the expandable polystyrene resin particles of the present invention to the absorbance at the center of the particle particles (B) is satisfied (A). <(B) and (A) is a relationship of 〇. 5 or more. In the case of the foamed polystyrene-based resin particles of the present invention, the ratio of the ethylene-acrylate-based copolymer component contained in the particles of the particles tends to be low at the surface layer side. Further, in the surface layer portion, a certain ester acetate copolymer component is also present. ^—The foamed polystyrene-based resin particles of the fluorinated resin have a distribution structure such as a pre-ene acrylate-based copolymer component, so that even if the pressure of the water-strip gas at the time of molding is low, When a foamed molded body having a beautiful appearance is obtained, even when it is molded at a high vapor pressure of 15 320980 200938572, a foamed molded body which is less likely to be deteriorated in heat resistance due to a decrease in heat resistance can be obtained. Satisfied (A) <(B) and (A) is 0.05 or more. In the case of the system, it is difficult to obtain the aforementioned effects. The range of the range of from 0.08 to 0.47 is more preferably in the range of from 0.05 to 0.50.范围内范围内。 The range of the range of 0. 20 to 0. Furthermore, the ratio of the absorbance ratios (A) to (B) (B/A) is in the range of 1.10 to 3.00, more preferably in the range of 1.17 to 2.88.发泡 The expandable polystyrene resin particles of the present invention can be efficiently produced by the above-described production method of the present invention, but the production method is not limited thereto. The foamable polystyrene resin particles of the present invention are preliminarily foamed so as to have a bulk density of from 0.01 to 0. 033 g/cm 3 to form preliminary expanded particles, and further to fill the preliminary expanded particles. In the cavity of the forming mold, it is heated and subjected to in-mold foam molding, and the crucible can be used for producing a blister foam molded body. [Examples] Hereinafter, specific examples of the present invention are shown by way of examples, but the following examples are merely illustrative of the present invention, and the present invention is not limited to the following examples. Further, in the following examples and comparative examples, the results of the absorbance ratio of the expandable polystyrene-based resin particles were the same as those of the polystyrene-based resin before the impregnation of the foaming agent. Example 1 16 320980 200938572 (Manufacture of seed particles) In a polymerization vessel with a stirrer having a content of 1 GG liter, 40,000 g of water was supplied, and the third scale (four) l〇〇g as a suspension stabilizer was used as an anionic interface activity. The dodecyl benzoic acid 332. (10), while stirring, adding styrene 4〇_g, as a polymerization initiator, Weihua benzoic acid 96.0g and third butyl peroxide After the purpose of (10), the temperature was raised to 90 C to polymerize. Then, it was kept at this temperature for 6 hours, and further heated to 125 C and kept at 2 hours 8 ′. Thereafter, it was cooled to obtain polystyrene resin (Ά. _ divided into the above-mentioned polystyrene resin particles (4), and obtained The polystyrene resin particles (6) having a particle diameter of 0.5 to 0.71 Å. Next, in a polymerization container with a 5 liter content and a search machine, 2GG0g of water and the above-mentioned polystyrene resin particles are supplied. (6), as a suspension stabilizer, the coke dish acid town 6. 0 § and as an anionic surfactant, the tetra- 4 phenyl lysine red Gg, - money mixed, - warmed to the muscle. ❿ (1st polymerization step): then 'Dissolving 1.5 g of peroxybenzoic acid (4) and butyl peroxybenzene m as a polymerization initiator in benzene (10) for parts by mass of 36 parts by mass) and butyl parts by mass of 6 parts by mass) The mixture was supplied to the above-mentioned =liter polymerization vessel and kept at 75 t for 6 q minutes. (Second polymerization step) After 60 minutes, the reaction was simultaneously carried out using a pump to raise the styrene 29 〇g solution to 11 (TC) for 150 minutes, and quantitatively supplied to 320980 17 200938572 in the poly S bar. Then, the temperature is raised to 120. (:: After 2 hours, it is cooled) to obtain polystyrene resin particles (c). (Absorbance ratio of resin particles) The obtained polystyrene resin particles (c) The absorbance ratio (A) of the surface of the resin particles and the absorbance ratio (B) of the center enthalpy were measured according to the following <Measurement of absorbance ratio>. The results are shown in Table 1. Further, the absorbance ratio (A) was calculated. The ratio of (B) ((B)/(A)) is also shown in Table 1. Further, for the obtained foamable polystyrene resin, the following is also < 吸 Absorbance ratio measurement> The absorbance ratio was measured. (Measurement of absorbance ratio) The absorbance ratio (D17 3 0 / D16 0 0 ) was measured in the following manner. That is, 'the ATR method is used for the surface of each of the resin particles (the payee A in Fig. 1) and the center of the cross section cut by the center of the particle (the pay B in Fig. 2) Infrared spectroscopic analysis performed on the surface of the particles to obtain an infrared absorption spectrum. ❹ ° and luminosity ratio (D1730/D1600) were calculated from the respective infrared absorption spectra, and the average of the absorbance ratios calculated for the surface a was taken as the absorbance ratio (A), and the absorbance ratio calculated for the center portion b was added. The average is taken as the absorbance ratio (B). The absorbances D1730 and D1600 are measured, for example, using a measuring device sold by Nicolet under the trade name "Fully Leaf Transform Infrared Spectrophotometer MAGMA 560". Further, the absorbance Μ 600 of 1600 cm-1 obtained from the infrared absorption spectrum refers to the in-plane vibration derived from the benzene ring contained in the polystyrene resin. 18 320980 200938572 » The action is 600CBT1 attached to the household The height of the peak that appears. • In addition, the absorption from the infrared absorption D1730 refers to the absorbance from the 73 〇cm passed by the acrylic acid. The vibration of the vibration between the (10) base of the 丽^W(3) base greets the height of the peak appearing. (Foaming agent impregnation) Next, in another 曰Pie _, a water supply 22 〇〇S, a polymerization container equipped with a stirrer, a polyethylene resin particle (c) 18 〇〇 g, as 1 The stabilizer (4) _ heart and 12 乍 are stirred while stirring, and the temperature is raised to 7 nv, A ^ i · 0 light, C. 6-g is used as a foaming aid to add 27.0 g of hexane and 2,6 g of diisobutyl phthalate as a ring plasticizer. The 6 g is placed in a sealed container and sealed, and the liter (5) is placed in ^ 歼 / dish to i〇oc. Secondly, 90g of n-butane as a hairpin is pressed into the gentleman's narration β / θίχ / package of human six. .匕 Set the polystyrene resin particle (c) in the poly-bene and keep 3,j, n* AL· .r\ λ ο After the 'cold clock to 3 〇 C or less and then take it out of the polymerizer , dried thorns ^ ° ^ foaming polystyrene tree tree particles. Example 2 _ In addition to the first polymerization step, the peroxidic sulfhydryl group as a polymerization initiator, 6.8 g and the third butyl benzoate phthalic acid g | h 5 g were dissolved in 200 g of ethylene (relatively In the same manner as in Example i, a foamed ethylene was obtained in the same manner as in Example i, except that 1 part by mass of the plate was used in an amount of 4 parts by mass) and 1 Gg of propylene (1 part by mass to 2 parts by mass). Resin particles. In the same manner as in Example 1, the polystyrene resin particles (C) before impregnation of the foaming agent were measured for the absorbance ratio (Α) of the surface of the ζ, 彡 j疋 and the absorbance at the center portion. 320980 19 The results of 200938572 are shown in Table 1. (8), and calculate the ratio ((8)/(A)). Example 3 ^ 〇 〇 稀 稀 56 56 56 56 56 56 56 56 56 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 In the same manner as in Example 1, the ratio of the absorbance ratio (A) of the surface to the absorbance (B) of the center portion of the polystyrene-based resin particles (c) before impregnation of the foaming agent was measured, and the ratio was calculated. ((B)/(A)). The results are shown in Table 丨^. Example 4 In addition to the first polymerization step, benzoyl peroxide 6.8, which is a polymerization initiator, and 8 butyl peroxybenzoate 15 were dissolved in 40 g of styrene (relative to the seed particles). 1 part by mass of 8 parts by mass), 30 g of butyl acrylate (6 parts by mass relative to 1 part by mass of the seed particles); and in the second polymerization step, the temperature is raised at 15 minutes. The expandable polystyrene resin particles were obtained in the same manner as in Example 1 except that the amount of styrene supplied to the polymerization vessel by the pump was 143 gram. In the same manner as in Example 1, the ratio of the absorbance ratio (A) of the surface of the polyphenylene-based resin particles (c) before impregnation of the foaming agent to the absorbance ratio (B) of the center portion was calculated and calculated. (B)/(A)). The results are shown in Table 1. 5克溶苯苯苯苯苯苯苯苯苯苯苯苯苯苯苯苯苯苯苯苯苯苯苯苯苯苯苯苯苯苯苯苯苯苯苯苯苯酯360 g (72 parts by mass based on 100 parts by mass of the seed particles), 30 g of butyl acrylate (6 parts by mass relative to 100 parts by mass of the seed particles); and 150 in the second polymerization step The foaming polyphenylene-based resin particles were obtained in the same manner as in Example 1 except that the styrene supplied to the polymerization vessel was quantitatively added in a minute. In the same manner as in the first embodiment, the ratio of the absorbance ratio (A) of the surface to the absorbance (B) of the center portion of the polystyrene resin particles (C) before impregnation of the foaming agent was measured, and the ratio was calculated. ((B)/(A)). The results are shown in Table i. Example 6 In addition to the first polymerization step, the type of acrylate used was changed to ethyl acrylate, and the peroxymethyl sulfonyl group and the third butyl peroxybenzoate were used as a polymerization initiator. Ug is dissolved in a mixed solution of styrene i7〇g (34 parts by mass based on 100 parts by mass of the seed particles) and B. 4 〇g of acrylic acid (8 parts by mass based on 100 parts by mass of the seed particles). The foaming polystyrene resin particles were obtained in the same manner as in the Example except that the amount of the stupid vinyl monomer to be supplied to the polymerization vessel was 1290 g. In the same manner as in Example 1, the absorbance ratio (A) of the surface and the absorbance at the center portion (B) of the polystyrene-based sapphire particles (c) before impregnation of the foaming agent were measured, and these were calculated. Ratio ((B)/(A)). The results are shown in Table ^. Example 7 320980 21 200938572 In addition to dissolving 6 8 g of a peroxyl base as a polymerization initiator and 15 g of a first butyl peroxybenzoate in a stupid vinyl monomer 18, butyl acrylate 30 g In the mixed liquid, the temperature was raised at 15 minutes, and the styrene-based monomer supplied to the polymerization vessel in a pump-to-human amount was set to 75 〇g, and the foaming polymerization was obtained in the same manner as in Example 1. Styrene resin particles. In the same manner as in the example 1, the ratio of the absorbance ratio (A) of the surface of the polystyrene resin particles (C) before impregnation of the foaming agent to the absorbance ratio (B) of the center portion was measured, and the ratio was calculated (( B) / (A)). The results are shown in Table 1.实施 Example 8 In addition to the benzoyl benzoate group as a polymerization initiator, 6.8 g and the second butyl peroxyformate 1·5 g were dissolved in a styrene monomer 18 〇g, butyl acrylate 30 g The mixture was heated at a temperature of 15 minutes, and the styrene-based monomer which was supplied to the polymerization vessel by a pump was used in an amount of 2 〇〇〇g, and the foaming was carried out in the same manner as in Example 1. Polystyrene resin particles. In the same manner as in the example 1, the ratio of the absorbance of the surface of the polystyrene resin particles (c) before the impregnation of the foaming agent to the absorbance of the center portion (Β) was calculated and the ratio was calculated (( Β)/(Α)). The results are shown in Table 1. Example 9 In addition, 1.5 g of benzoyl peroxide group as a polymerization initiator and 1.5 g of a third butyl peroxyformate were dissolved in a mixture of styrene monomer i80 g and butyl acrylate 30 g. The temperature was raised in 15 minutes, and the styrene monomer which was quantitatively supplied to the polymerization vessel by the pump was set to 5 〇〇g to 22 320980 200938572, and the foaming polystyrene system was obtained in the same manner. And implement you] resin particles. : 2 1 is the same as the polystyrene system before impregnation of the foaming agent: the ratio of the absorbance of the fixed surface (4) to the absorbance of the central portion is different ((b)/( a)). Table of the results ίο τ In addition to dissolving benzoyl peroxide 6.8 g and butyl benzoic acid benzoate 1.3⁄4 as a polymerization initiator in a styrene monomer 18 〇 In the mixture of g and butyl acrylate 30 g, the temperature was raised in 150 minutes, and the styrene-based monomer which was supplied to the polymerization vessel by the pump was quantitatively set to 275 〇g, and the rest was the same as in Example 1. The foamable polystyrene-based resin particles were obtained. In the same manner as in Example 1, the ratio of the absorbance ratio (A) of the surface to the absorbance at the center portion of the polyphenylene-based resin particles (c) before impregnation of the foaming agent was measured. (B), again, the ratio of these is ((b)/(A)). The results are shown in Table 1. φ Comparative Example 1 In Example 1, 'except for the use of acrylic acid in the first polymerization step Ester, and 1.5 g of peroxymethyl sulfonyl group and 1.5 g of t-butyl peroxybenzoic acid vinegar were set to 210 g of styrene (relative to the mass of the seed particles) In the same manner as in Example 1, foamed polystyrene-based resin particles were obtained in the same manner as in Example 1. In the same manner as in Example 1, the polyphenylene-based resin particles before impregnation with the foaming agent were C) Measure the ratio of the absorbance of the surface (A) to the absorbance ratio of the center (B), and calculate the ratio ((b)/(a)). The results are shown in Table i. 320980 23 200938572 Comparative Example 2 - In addition to the first polymerization step, 6.8 g of methyl peroxide peroxide and 1.5 g of t-butyl peroxybenzoate as a polymerization initiator were dissolved in stupid ethylene 202 g (relative to the mass of the seed particles) 4 parts by mass of 4 parts by mass), C: 8 g of butyl vinegar (1.6 parts by mass relative to 100 parts by mass of the seed particles), and in the second polymerization step, the temperature is raised for 150 minutes, and In the same manner as in Example 1, the foaming polystyrene-based agglomerated particles were obtained in the same manner as in Example 1 in the same manner as in Example 1. The same applies to the foaming agent. (b) The absorbance ratio (a) and center of the surface of the polystyrene acetaminophen before the impregnation The absorbance ratio (B) 'again' calculates the ratio ((B) / (A)). The results are shown in Table 1. Comparative Example 3 ^ In addition to the polymerization initiator in the first polymerization step The peroxidized benzoyl amide group 6·8g and the third butyl benzoate benzoate i.5g are dissolved in the sufficiency 140g (28 parts by mass relative to the seed particles), and the two bindings are 70 g of ester (14 parts by mass relative to 1 part by mass of the seed particles); and in the second polymerization step, the temperature is raised in 150 minutes, and the benzene is quantitatively supplied to the polymerization vessel in the range of 1 time. The foamable polystyrene resin particles were obtained in the same manner as in Example 1 except that the ethylene content was 1,290 g. In the same manner as in Example 1, the ratio of the absorbance ratio (A) of the surface to the absorbance (δ) of the center portion of the polystyrene resin particles (c) before impregnation of the foaming agent was measured, and the ratio was calculated. (B)/(A)). The results are shown in Table 1. 24 320980 200938572 „ Comparative Example 4 In addition to the polymerization process in the first ..»β Ο polymerization, the peroxymethyl ketone group as a polymerization initiator 6. 8g and Chu _ 7 private on ^ military tributyl benzoate 1.5 g of formic acid vinegar was dissolved in 30 g of stupid ethylene (6 parts by mass relative to strong + ___ Qn and 100 parts by mass of seed particles), and 30 g of butyl acrylate (relative to 潴, ^ ^, and 1 part by mass of the uncle) a mixture of T; and in the 25th 8 μ ks step, the temperature is raised in 150 minutes, and the styrene supplied to the polymerization vessel by pumping is adjusted to 1440 parts by mass, and the rest The foaming polystyrene tree 'lipid particles were obtained in the same manner as in Example 5, , and Example 1. The same as in Example 1, the same as _iL.,. J, before impregnation of the blowing agent The ratio of the absorbance of the polystyrene-bonded tree sapphire particles (e)/receiving surface (a) to the surface of the towel (B), and the ratio of (B)/(A). The result is shown in Table I. In the first polymerization step, the benzoyl peroxide 6.8 g and the third butyl peroxybenzoic acid vinegar as a polymerization initiator were dissolved in 1. 5 g. benzene ® 460 g (92 parts by mass based on 100 parts by mass of the seed particles), 30 g of butyl acrylate (6 parts by mass relative to 100 parts by mass of the seed particles); and in the second polymerization step, 150 In the same manner as in Example 1, the foaming polystyrene resin particles were obtained in the same manner as in Example 1 except that the amount of styrene supplied to the polymerization vessel by the pump was 1010 parts by mass. Similarly, the ratio of the absorbance ratio (A) of the surface to the absorbance (B) of the center portion of the polystyrene resin particles (c) before impregnation of the foaming agent is calculated, and the ratio (b)/ is calculated. (a)). The results are shown in Table 1. 25 320980 200938572 Comparative Example 6 In a polymerization vessel equipped with a stirrer having a content of 5 liters, water was supplied. 2000 parts by mass of the above-mentioned polystyrene resin particles (B) 500 The mass fraction, 6.0 parts by mass of magnesium pyrophosphate as a suspension stabilizer, and 0.3 parts by mass of the decyl benzoate as an anionic surfactant, and the temperature is raised to 75 ° C while being disturbed. Made of 1470 parts by mass of styrene and 30 masses of butyl acrylate The mixture is used in an amount of 210 parts by mass (100 parts by mass of the seed particles, styrene is 41.2 parts by mass, butyl acrylate is 0.784 Å by mass), and the mass of benzoyl peroxide is dissolved. And 5 parts by weight of the third butyl peroxyformate, after being supplied to the above-mentioned 5 liter polymerization vessel, and kept at 75 ° C for 60 minutes. After 60 minutes, the reaction liquid was heated for 150 minutes. At 110 ° C, 1290 parts by mass of the mixture of the styrene-based monomer and butyl acrylate was supplied to the polymerization vessel in a 150-minute manner using a pump, and then the temperature was raised to 120 ° C, and after 2 hours, it was cooled. The styrene resin particle q (c) was obtained. Thereafter, foamable polystyrene resin particles were obtained in the same manner as in Example 1. In the same manner as in the example 1, the ratio of the absorbance ratio (A) of the surface to the absorbance (B) of the center portion of the polystyrene resin particles (c) before impregnation of the foaming agent was measured, and the ratio of these was calculated (( B) / (A)). The results are shown in Table 1. 26 320980 200938572 . [Table 1]
27 320980 200938572 如表1所示，在本發明之實施例1至10中，聚笨乙烯 · 系樹脂粒子之表面的吸光度比（A)與中心部之吸光度比（B) . 係滿足（A)<(B)且（A)為0. 05以上之關係。 又，在實施例1至10中，吸光度比（A)為0. 05至0. 50 的範圍内，且前述吸光度比（B)為0. 20至0. 60的範圍内。 進一步，在實施例1至10中，吸光度比（A)與（B)之比 (B/A)為1. 10至3. 00的範圍内。 另一方面，在比較例1中，因未加入丙烯酸醋，故無 法測定源自於酯基之吸收的1730〇11_1之吸光度D1730。 Ο 又，在比較例2中，因第1聚合步驟所使用之丙烯酸 丁酯之量少，故表面之吸光度比（A)為0. 02，未達本發明 所規定之表面的吸光度比（A)之下限（0. 05)。 又，在比較例3中，因第1聚合步驟所使用之丙烯酸 丁酯之量多，故表面的吸光度比（A)變成大於中心部之吸光 度比（B)。 又，在比較例4中，因第1聚合步驟所使用之苯乙烯 0 之量少，故表面的吸光度比（A)變成大於中心部之吸光度比 (B)。 又，在比較例5中，因第1聚合步驟所使用之苯乙烯 之量多，故表面之吸光度比（A)為0. 04，未達本發明所規 定之表面的吸光度比（A)之下限（0. 05)。 又，在比較例6中，因在第2聚合步驟中使用苯乙烯 以及丙烯酸丁酯，俾表面的吸光度比（A)變成大於中心部之 吸光度比（B)。 28 320980 200938572 (預備發泡、發泡成形） 如前述般所製造之在13°C以下保管5天後之實施例1 至10及比較例1至6各別的發泡性聚苯乙烯系樹脂粒子， 在對於其粒子表面以硬脂酸鋅及羥基硬脂酸三甘油酯作為 表面處理劑進行被覆處理之後，以預備發泡裝置進行預備 發泡直到成為體密度0. 〇167g/cm3，然後以2〇它使其熟成 24小時而得到預備發泡粒子。 ❹ /其次’於具備具有内尺寸別〇mmx40〇mmx30imn之長方體 形狀的模之成形楔的發泡粒自動成形機的模穴内填充前 述預備發錄=，以下述之2條件（成形蒸氣壓），進行密 度0. 0167g/cm的聚笨乙烯系樹脂發泡 之 ACE-3SP) 成形條件（機為積拉機製作賴份公㈣ 成形蒸氣壓 2條件（壓力計壓：〇, 模具加熱 5秒 一方加熱 (設定壓力0. 03MPa) 另一方加熱 3秒 兩面加熱 15秒 以水冷卻 5秒 放置冷卻 (真空放置冷卻、QS 取出設定面壓 〇.02MPa 對於使用實施例 1至10、及比較例1 性聚苯乙稀系樹月旨缸子而製造的成形時水蒸 '之發、; 0. 04MPa時之發泡成形體、與成形時氧厭聲為 4壓為 〇.〇9MPa 32〇98〇* 29 200938572 時之發泡成形體，使用以下所示之條件，調查其彎曲強度、 ， 發泡成形體外觀、冷卻時間而評估。其結果記載於表2。 (彎曲強度之測定） 對於實施例（及比較例）所得到之發泡成形體，依據JIS A9511 = 2006「發泡塑膠保溫材」記載之方法而測定彎曲強 度。 亦即’使用Tensilon萬能試驗機UCT-10T(Orientec 公司製），以試驗體尺寸為75mmx300mmx50mm，壓縮速度為 10mm/分鐘，前端夾具（jig)為加壓楔子10R、支撐台10R， 〇 支撐間距離200mm之條件測定，並以下式算出彎曲強度。 試驗片之數目為3個，求出其平均值。 彎曲強度（MPa)=3 FL/2bh2 (此處’ F表示彎曲最大荷重（n) ’ L表示支點間距離 (mm) ’ b表示試驗片之寬（mm)，h表示試驗片之厚度(腿。 (發泡成形體外觀之評估） 以目視確認發泡成形體之表面，依據以下之評估基準 而進行評估。 〇 〇：外觀美麗且於發泡粒子間無間隙者。 X:於發泡粒子間之間隙多或產生熔融者。 (冷卻時間） 本發明之冷卻時間係在以前述記載之成形條件成形 時，從水冷步驟終止後直到模穴内之成形體的發泡壓成為 取出設定面壓〇· 〇2MPa為止之放置冷卻時間作為冷卻時 間。冷卻時間係以每一條件（成形蒸氣壓）各成形3片，作 320980 30 · 200938572 * . 為其平均值。 -(綜合評估） 依據其次之評估基準，進行綜合評估。 ◎:在成形時之水蒸氣壓為0. 〇4MPa之情形、為〇. 〇9MPa 之情形的兩者，所得到之發泡成形體的外觀均為美麗 者。 X :在成形時之水蒸氣壓為0.04MPa之情形、為0.09MPa 之情形的至少一者，其發泡成形體之外觀為差者。 31 320980 200938572 綜合 評估 [ 1_ @ @ ◎ @ ◎ @ ◎ © X X X X X 1泡成形體之特性 0 0 9MPa成形 冷卻時間（秒） r· Ο) 兮 r- »— ιη 产 σι 寸 Τ" CM ΙΟ CO t/> t— N \〇 T— CO tr> r· OJ ω T~* CO ΙΛ τ— tn τ— Φ ID r— <0 CO 1— ¢0 T~ tf) U) r— 0) eg T- 彎曲強度(MPa) 寸 <r> 寸 to ιη η 1Ω CO η to 叶 CO ID CO 寸 n tn n CO CO CO CO O) CM 卜 Csl CO CO N N 成形艎外觀 〇 Ο ο 〇 ο O o 〇 O O 〇 〇 X X o' X 0，0 4MPa成形 j冷卻時間（秒） in ο τ— σ> ο Τ- U> ο 产 0) Ο t— 寸 Ο t— csi 〇 t— 〇 r* CO o 〇 *— CO o r- 〇 τ— rt r- r- L0 τ- r· 1 0 9 好 τ— f·— t— 彎曲強度(MPa) 0¾ rt CM Ο C0 寸 <0 « CO 寸 ro co o CO o CD C3 <0 CO <0 M CC <S n CO CO M in N CO 成形體外觀 ο ο 0 〇 ο 〇 O 〇 〇 〇 K X 〇 X X 〇 實施例1 I實施例2 實施例3 實施例4 實掩例5 實施例6 實施例7 實施例8 實施例9 實施例1 0 比較例1 比較例2 比較例3 比較例4 比較例5 比較例6 ❹ Ο 32 320980 200938572 從表2之結果可知，在第1聚合步驟中，相對於種粒 泰 子100質量份供給苯乙烯7. 0至80. 0質量份與丙烯酸酯 2. 0至12. 0質量份，使種粒子吸收此等單體並聚合而使種 粒子成長的本發明之實施例1至10中，在成形時為低的水 蒸氣壓（〇. 〇4MPa)及為高的水蒸氣壓（0. 09MPa)之任一情形 下，均可得到外觀美麗且彎曲強度高之發泡成形體。 另一方面，使第1聚合步驟使用之單體只為苯乙烯而 未添加丙稀酸i旨之比較例1，其藉由低的水蒸氣壓（0. 04MPa) ® 之成形所得到的發泡成形體之外觀差，且彎曲強度低。 於第1聚合步驟中以未達本發明之範圍的量添加丙烯 酸醋之比較例2，其藉由低的水蒸氣壓（0. 04MPa)之成形所 得到的發泡成形體之外觀差，且彎曲強度低。 於第1聚合步驟的丙烯酸酯之量超過本發明之範圍的 比較例3，其藉由高的水蒸氣壓（0. 09MPa)之成形所得到的 發泡成形體之外觀差，且彎曲強度低。 Q 於第1聚合步驟的苯乙烯之量未達本發明之範圍的比 較例4，其藉由低的水蒸氣壓（0. 04MPa)及高的水蒸氣壓 (0. 09MPa)之兩者之成形所得到的發泡成形體外觀均差，且 彎曲強度變低。 於第1聚合步驟的苯乙烯之量超過本發明之範圍的比 較例4，其藉由低的水蒸氣壓（0. 04MPa)之成形所得到的發 泡成形體之外觀差，且彎曲強度變低。 在第1聚合步驟及第2聚合步驟之兩者中使用苯乙烯 與丙稀酸S旨之混合物的比較例6，其藉由高的水蒸氣壓 33 320980 200938572 且彎曲強 (0. 09MPa)之成形所得到的發泡成形體之外觀差 度變低。 (預備發泡粒子之保存性的比較） 與前述⑽備發泡、發泡成形)之情形同樣 例1至10、及比較例1至6各别的發泡性 ^ 粒子的表面上以硬脂酸鋅隸基旨酸三甘油旨 處理劑進行被覆處理之後’彳f發泡裝置進行 直到成為體密度0. 0l67g/cm。 在預備發泡後，使所得到之各預備發泡粒子於3〇它、 濕度50%之環境下放置7日。 其次’於具備具有内尺寸300mmx4OO顏x3〇mm之長方體 形狀的模穴之成形模的發泡粒自動成形機的模穴内填充前 述預備發泡粒子，以下述之條·件，進行密度〇. 〇167g/cm3 的聚苯乙烯系樹脂發泡成形體之成形。 成形條件（成形機為積水工機製作所股份公司製之ACE-3SP) 成形蒸氣壓 壓力計壓：0. 〇4MPa 模具加熱 5秒 一方加熱 (設定壓力〇· 〇3MPa) 另一方加熱 3秒 兩面加熱 15秒 以水冷卻 5秒 放置冷卻 (真空放置冷卻、QS成形模式） 取出設定面壓 0.02MPa 對於使用以預僙發泡粒子之狀態放置7日後之各別之 320980 〇 34 200938572 , 預備發泡粒子並以成形時水蒸氣壓為0. 04MPa而製造之實 • 施例1至10及比較例1至6之各別的發泡成形體，與前述 (預備發泡、發泡成形）之情形相同地，調查其彎曲強度、 發泡成形體外觀、冷卻時間而評估。又.，综合評估係依據 下述之評估基準而進行綜合評估。其結果表示於表3。 (綜合評估） ◎:所得到之發泡成形體的外觀美麗者。 X :發泡成形體的外觀差者。 ❹[表3]27 320980 200938572 As shown in Table 1, in the examples 1 to 10 of the present invention, the ratio of the absorbance of the surface of the polystyrene resin particles (A) to the absorbance of the center portion (B) is satisfied (A). <(B) and (A) is a relationship of 0.05 or more. The range of the absorbance ratio (B) is in the range of from 0.20 to 0.60, and the absorbance ratio (B) is in the range of from 0.20 to 0.60. Further, in the examples 1 to 10, the ratio of the absorbance ratios (A) to (B) (B/A) is in the range of 1.10 to 3.00. On the other hand, in Comparative Example 1, since the acrylic acid vinegar was not added, the absorbance D1730 of 1730〇11_1 derived from the absorption of the ester group could not be measured. Further, in Comparative Example 2, the amount of butyl acrylate used in the first polymerization step was small, so the absorbance ratio (A) of the surface was 0.02, and the absorbance ratio of the surface not specified in the present invention was (A). The lower limit of the (0. 05). Further, in Comparative Example 3, since the amount of the butyl acrylate used in the first polymerization step was large, the absorbance ratio (A) of the surface became larger than the absorbance ratio (B) of the center portion. Further, in Comparative Example 4, since the amount of styrene 0 used in the first polymerization step was small, the absorbance ratio (A) of the surface became larger than the absorbance ratio (B) of the center portion. Further, in Comparative Example 5, since the amount of styrene used in the first polymerization step was large, the absorbance ratio (A) of the surface was 0.04, and the absorbance ratio (A) of the surface not specified in the present invention was Lower limit (0. 05). Further, in Comparative Example 6, since styrene and butyl acrylate were used in the second polymerization step, the absorbance ratio (A) of the surface of the crucible became larger than the absorbance ratio (B) of the center portion. 28 320980 200938572 (Preparation foaming, foam molding) Each of the foaming polystyrene resins of Examples 1 to 10 and Comparative Examples 1 to 6 which were produced after the storage at 13 ° C or lower for 5 days as described above The particle, after the surface of the particle is coated with zinc stearate and hydroxystearic acid triglyceride as a surface treatment agent, the foam is pre-foamed by a preliminary foaming device until the bulk density is 0. 〇 167 g / cm 3 , and then The pre-expanded particles were obtained by subjecting it to 2 hours for 24 hours. ❹ / Next 'In the cavity of the foamed pellet automatic forming machine having the forming wedge having the rectangular shape of the inner dimension 〇mmx40〇mmx30imn, the above-mentioned preliminary registration = in the following two conditions (forming vapor pressure), ACE-3SP, which is foamed with a polystyrene resin having a density of 0. 167 g/cm. The molding conditions (the machine is made by a laminator) (4) Forming vapor pressure 2 conditions (pressure gauge pressure: 〇, mold heating for 5 seconds) Heating (set pressure 0. 03 MPa) The other side is heated for 3 seconds, heated on both sides for 15 seconds, cooled by water for 5 seconds, placed and cooled (vacuum placed, cooled, QS taken out, set surface pressure 〇. 02 MPa, using Examples 1 to 10, and Comparative Example 1 When the polystyrene tree is used for the steaming of the forming cylinder, the foamed molded body at 0. 04 MPa and the oxygen-induced sound during molding are 4 〇. 9MPa 32〇98〇* 29 200938572 The foamed molded article was evaluated by the following conditions, and the flexural strength, the appearance of the foamed molded article, and the cooling time were evaluated. The results are shown in Table 2. (Measurement of Bending Strength) For the examples ( And comparative examples) The foamed molded body was measured for bending strength according to the method described in JIS A9511 = 2006 "foamed plastic heat insulating material". That is, 'Tensilon universal testing machine UCT-10T (manufactured by Orientec) was used, and the test body size was 75 mm x 300 mm x 50 mm. The compression speed was 10 mm/min, and the front end jig (jig) was a pressure wedge 10R, a support table 10R, and the distance between the support and the support was 200 mm, and the bending strength was calculated by the following formula. The number of test pieces was three, and the result was obtained. Average value. Bending strength (MPa) = 3 FL/2bh2 (where 'F is the maximum bending load (n) ' L is the distance between the fulcrums (mm) ' b is the width of the test piece (mm), and h is the test piece. Thickness (leg. (Evaluation of the appearance of the foamed molded body) The surface of the foamed molded body was visually confirmed and evaluated according to the following evaluation criteria. 〇〇: The appearance was beautiful and there was no gap between the expanded particles. The gap between the expanded particles is large or melted. (Cooling time) The cooling time of the present invention is formed by the foaming of the molded body in the cavity after the completion of the water cooling step in the molding conditions described above. In order to take out the set cooling time of the set surface pressure 〇·〇2 MPa as the cooling time, the cooling time is formed into three pieces for each condition (forming vapor pressure), and is 320980 30 · 200938572 * . Evaluation) A comprehensive evaluation is carried out based on the next evaluation criteria. ◎: The water vapor pressure at the time of molding is 0. 〇4 MPa, and both of them are 〇. 9 MPa, and the appearance of the obtained foamed molded body is For the beautiful. X: At least one of the case where the water vapor pressure at the time of molding is 0.04 MPa and the case of 0.09 MPa, the appearance of the foamed molded article is inferior. 31 320980 200938572 Comprehensive evaluation [ 1_ @ @ ◎ @ ◎ @ ◎ © XXXXX 1 Characteristics of the foamed body 0 0 9MPa Forming cooling time (seconds) r· Ο) 兮r- »— ιη σ ι Τ quot quot; CM ΙΟ CO t /> t— N \〇T—CO tr> r· OJ ω T~* CO ΙΛ τ— tn τ— Φ ID r— <0 CO 1— ¢0 T~ tf) U) r— 0) eg T-bending strength (MPa) inch <r> inch to ιη η 1 Ω CO η to leaf CO ID CO inch n tn n CO CO CO CO O) CM 卜 Csl CO CO NN Forming 艎 Appearance 〇Ο ο 〇ο O o 〇OO 〇〇XX o' X 0,0 4MPa forming j cooling time (seconds) in ο τ— σ> ο Τ- U> ο production 0) Ο t—inch Ο t— csi 〇t— 〇r* CO o 〇*— CO o r- 〇τ— rt r- r- L0 τ- r· 1 0 9 good τ—f·—t— bending strength (MPa) 03⁄4 rt CM Ο C0 inch <0 « CO inch ro co o CO o CD C3 <0 CO < 0 M CC <S n CO CO M in N CO Shape of the formed body ο 0 〇ο 〇O 〇〇〇KX 〇XX 〇Example 1 I Example 2 Example 3 embodiment 4 real mask 5 embodiment 6 embodiment 7 embodiment 8 embodiment 9 implementation 1 0 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 ❹ Ο 32 320980 200938572 From the results of Table 2, it was found that in the first polymerization step, styrene was supplied in 100 parts by mass relative to the seed granules. 7. In the present invention, in Examples 1 to 10, in the forming of the present invention, in the case of the present invention, in the case of the present invention, the present invention In any case of a low water vapor pressure (〇. MPa 4 MPa) and a high water vapor pressure (0. 09 MPa), a foam molded article having a beautiful appearance and high bending strength can be obtained. On the other hand, the monomer used in the first polymerization step was only styrene and the acrylic acid was not added. Comparative Example 1 was obtained by forming a low water vapor pressure (0.04 MPa) ® . The shape of the foamed article is poor and the bending strength is low. Comparative Example 2 in which acryl vinegar was added in an amount not exceeding the range of the present invention in the first polymerization step, and the appearance of the foamed molded article obtained by molding with a low water vapor pressure (0.04 MPa) was poor, and Low bending strength. In Comparative Example 3 in which the amount of the acrylate in the first polymerization step was more than the range of the present invention, the foamed molded article obtained by molding with a high water vapor pressure (0.03 MPa) had poor appearance and low bending strength. . Q, Comparative Example 4 in which the amount of styrene in the first polymerization step is less than the range of the present invention, which is a combination of a low water vapor pressure (0.04 MPa) and a high water vapor pressure (0. 09 MPa). The molded foam obtained by the molding has a poor appearance and a low bending strength. In Comparative Example 4 in which the amount of styrene in the first polymerization step was more than the range of the present invention, the appearance of the foamed molded article obtained by molding with a low water vapor pressure (0.04 MPa) was poor, and the bending strength was changed. low. Comparative Example 6 using a mixture of styrene and acrylic acid S in both the first polymerization step and the second polymerization step, which was subjected to a high water vapor pressure of 33 320980 200938572 and a strong bending (0. 09 MPa). The appearance difference of the foamed molded body obtained by the molding becomes low. (Comparison of Preservation Properties of Prepared Foamed Particles) In the same manner as in the case of the above (10) foaming and foam molding), the surfaces of the foamable particles of Examples 1 to 10 and Comparative Examples 1 to 6 were hard fat. The zinc sulphate is subjected to a coating treatment of the acid triglyceride treatment agent, and then the 彳f foaming device is carried out until the bulk density is 0. 0l67g/cm. After preliminary foaming, each of the obtained preliminary expanded beads was allowed to stand in an environment of 3 Torr and a humidity of 50% for 7 days. Next, the above-mentioned preliminary expanded particles are filled in a cavity of a foamed automatic particle forming machine having a molding die having a rectangular parallelepiped shape having an inner dimension of 300 mm x 4 Å x 3 mm, and density is obtained by the following strips. The molding of a 167 g/cm3 polystyrene resin foam molded body. Molding conditions (Forming machine is ACE-3SP manufactured by Sekisui Kogyo Co., Ltd.) Forming vapor pressure gauge pressure: 0. 〇4MPa Mould heating for 5 seconds while one side is heated (set pressure 〇· 〇3MPa) The other side is heated for 3 seconds on both sides. 15 seconds, cooling with water for 5 seconds, cooling (vacuum placement cooling, QS forming mode). Take out the set surface pressure of 0.02 MPa. For the use of the pre-expanded foamed particles, the respective 320980 〇34 200938572 after the placement of the pre-expanded foamed particles, the pre-expanded particles And the foamed molded body of each of the examples 1 to 10 and the comparative examples 1 to 6 is the same as the above (pre-foaming, foam forming) in the case where the water vapor pressure at the time of molding is 0.04 MPa. The ground was evaluated for its bending strength, appearance of the foamed molded body, and cooling time. In addition, the comprehensive assessment is based on the following assessment criteria for a comprehensive assessment. The results are shown in Table 3. (Comprehensive evaluation) ◎: The appearance of the obtained foamed molded body is beautiful. X: The appearance of the foamed molded article is poor. ❹[Table 3]
發泡成形體之特性 0. 0 4MPa成形 综合評估 成形體外觀 彎曲強度(MPa) 冷卻時間（秒） 實施例1 〇 3. 3 10 0 ◎ 實施例2 〇 3. 1 9 9 © 實施例3 〇 3. 2 9 9 ◎ 實施例4 〇 3· 3 1 0 1 ◎ 實施例5 〇 3. 3 10 0 ◎ 實施例6 〇 3. 5 10 1 ◎ 實施例7 〇 3. 3 98 ◎ 實施例8 〇 3. 2 9 9 ◎ 實施例9 〇 3. 4 1 0 3 @ 實施例1 0 〇 3, 2 10 1 0 比較例Ί X 2, 1 8 9 X 比較例2 X 1. 9 8 8 X 比較例3 X 2, 2 9 2 X 比較例4 X 1, 9 9 7 X 比較例5 X 2. 0 8 7 X 比較例6 X 2, 2 ί 8 5 XCharacteristics of the foamed molded body 0. 0 4MPa Forming comprehensive evaluation of the molded body Appearance bending strength (MPa) Cooling time (seconds) Example 1 〇 3. 3 10 0 ◎ Example 2 〇 3. 1 9 9 © Example 3 〇 3. 2 9 9 ◎ Example 4 〇3· 3 1 0 1 ◎ Example 5 〇 3. 3 10 0 ◎ Example 6 〇 3. 5 10 1 ◎ Example 7 〇 3. 3 98 ◎ Example 8 〇 3. 2 9 9 ◎ Example 9 〇 3. 4 1 0 3 @ Example 1 0 〇3, 2 10 1 0 Comparative Example Ί X 2, 1 8 9 X Comparative Example 2 X 1. 9 8 8 X Comparative Example 3 X 2, 2 9 2 X Comparative Example 4 X 1, 9 9 7 X Comparative Example 5 X 2. 0 8 7 X Comparative Example 6 X 2, 2 ί 8 5 X
從表3之結果可知，本發明之實施例1至10即使使用 預備發泡後放置7日之預備發泡粒子，亦可藉由0,04MPa 35 320980 200938572 之低之成形時水蒸氣壓而得到外觀美麗的發泡成形 另一方面，在比較例1至θ中以與實施例:體 B寺無法得料觀美麗的發泡成形體。尤其'」、同之條件 泡、發泡成形）中，即使是如表2所示之以低二述巧備發 (0. 04MPa)可得到外觀良好之發泡成形體士私艮蒸氣壓 較例6，當使用預備發、泡後放置7日之預備發泡^比 亦無法得到外觀美麗的發泡成形體。 ’ 從此試驗結果可知，本發明之實施例 10戶斤才寻至ijFrom the results of Table 3, it is understood that Examples 1 to 10 of the present invention can be obtained by using a low vapor pressure at the time of forming of 0,04 MPa, 35,320,980, and 200938572, even if the pre-expanded particles placed for 7 days after preliminary foaming are used. On the other hand, in the comparative example 1 to θ, in the comparative example 1 to θ, the foamed molded body which was not beautiful in the form of the body B was not obtained. In particular, in the case of the same condition, foaming and foaming, even if it is as shown in Table 2, it can be obtained by using a low-profile preparation (0. 04 MPa) to obtain a foam molded body with a good appearance. In Example 6, a foamed molded article having a beautiful appearance could not be obtained by using a preliminary foaming ratio of 7 days after the preparation of the hair. From the results of this test, it can be seen that the embodiment of the present invention finds ij
預備發泡粒子的發泡力的保持性優異，保存性声好 [產業上之可利用性] 本發明之發泡性聚笨乙烯系樹脂粒子係適於製造用來 作為食品容器或捆包、緩衝材之聚苯乙烯系樹脂發泡成形 體。本發明之發泡性聚苯乙烯系樹脂粒子，其於成形時所 使用之水蒸氣的壓力即使為低壓，亦可得到外觀美麗且具 有高的強度之發泡成形體，故可謀求發泡成形體之製造成 本降低化、製造中之省能源化。 【圖面簡單說明】 第1圖係在以ATR法紅外線分光分析之發泡性聚笨乙 烯系樹脂粒子的吸光度比之測定中’表示發泡性聚苯乙烯 系樹脂粒子之表面的吸光度測定位置之示意圖。 第2圖係在以ATR法紅外線分光分析之發泡性聚苯乙 烯系樹脂粒子的吸光度比之測定中，表示發泡性聚苯乙烯 系樹脂粒子之中心部的吸光度測定位置之示意圖。 【主要元件符號說明】 36 320980 200938572 1 發泡性聚苯乙烯系樹脂粒子 A 表面 B 中心部 ❹ ❿ 37 320980The pre-foamed particles are excellent in the retention of the foaming power and have good storage properties. [Industrial Applicability] The foamable polystyrene-based resin particles of the present invention are suitable for use as food containers or bales. A polystyrene resin foam molded body of a cushioning material. In the foamable polystyrene resin particles of the present invention, even if the pressure of the water vapor used in the molding is low, a foamed molded article having a beautiful appearance and high strength can be obtained, so that foam molding can be achieved. The manufacturing cost of the body is reduced, and the energy saving in manufacturing is achieved. [Brief Description of the Drawings] Fig. 1 shows the position of the absorbance measurement on the surface of the expandable polystyrene resin particles in the measurement of the absorbance ratio of the foamable polystyrene resin particles analyzed by the ATR method. Schematic diagram. In the measurement of the absorbance ratio of the expandable polystyrene-based resin particles by the infrared spectroscopic analysis by the ATR method, the absorbance measurement position of the center portion of the expandable polystyrene resin particles is shown. [Explanation of main component symbols] 36 320980 200938572 1 Foamed polystyrene resin particles A Surface B Center ❹ ❿ 37 320980