1303643 玖、發明說明' 、、： (發明說明應敘明：發明所屬之技術領域、先前技術、內容、實施方式及圖式簡單說明） (一） 發明所屬之技術領域 本發明係有關一種搪塑成形用氯乙烯系樹脂糊、使用 它所成的成形物。 更詳言之，係有關一種搪塑成形時熱安定性優異、搪塑 成形用氯乙烯系樹脂糊之溶膠黏度適於實用的程度低、且 對成形物之玩具等所要求的丙烯腈-丁二烯-苯乙烯系樹脂 (ABS系樹脂）或聚苯乙烯系樹脂等而言非移行性優異、且 耐擴散性優異的氯乙烯系樹脂糊、使用它所成的成形物。 而且，本發明之搪塑成形用氯乙烯系樹脂糊係該業者 一般稱爲「糊溶膠」者。 (二） 先前技術 以往，氯乙烯系樹脂糊係在糊用氯乙烯系樹脂中配合作 爲可塑劑之芳香族羧酸酯製造使用。該芳香族羧酸酯中酞 酸酯系可塑劑、特別是酞酸雙（2 -乙基己酯）（以下稱爲DOP ) 具有較平衡的各物性，適於浸漬成形、塗覆成形、回轉成 形、螺旋成形、注模等之成形法，可使用於玩具、手袋、 壁紙或床材等之住宅內裝關係、底塗層或密封層等之汽車 關係、鋼板塗覆或帆布塗覆等之廣泛用途。 然而，於上述酞酸酯系可塑劑中恐會有擾亂內分泌作用 、且影響野生生物或人之生殖•發育的物質（所謂環境荷爾 蒙），故企求開發產業界動向之具有取代D0P等酞酸酯系可 1303643 塑劑之優異性能的可塑劑。 因此，例如部分用途中使用檸檬酸酯系可塑劑之乙醯基 檸檬酸三丁酯（ATBC)等作爲替代可塑劑’惟可塑劑本身之 耐加熱分解性不佳，在高溫條件下會有可塑劑之酸價上升 問題。 特別是玩具等多數採用的成形法之搪塑成形法係使搪塑 成形用氯乙烯系樹脂糊注入模具後加熱，且使多餘的未凝 膠化搪塑成形用氯乙烯系樹脂糊排出予以再利用，惟此時 所排出的搪塑成形用氯乙烯系樹脂糊之溫度通常上升40〜 1 00 °C，故要求僅耐反覆使用之熱安定性。 而且，任何習知之可塑劑就僅耐反覆使用的熱安定性而 言不充分。原因之一係因加熱使可塑劑分子中之烷基部分 氧化分解，因此造成可塑劑之酸價上升。 可塑劑之酸價對搪塑成形用氯乙烯系樹脂糊之黏度影響 極大，就加工性（熔融時之下垂、厚度之厚薄等）而言要求 安定性佳者。 因此，提案使用己二酸酯系可塑劑之己二酸二異壬酯 (DINA)的技術等，藉由該技術時雖可使初期黏度低黏度化 ，惟會有就耐加熱分解性、非移行性（對聚苯乙烯系樹脂等） 、耐擴散性等而言會有不充分的問題。 爲解決上述問題，有各種提案。 例如提案使用環己烷系羧酸酯作爲可塑劑之技術（例如 參照專利文獻1 )。然而，該技術就耐擴散性、非移行性（ 對ABS系樹脂、對聚苯乙烯系樹脂等）等而言雖佳，惟因可 1303643 塑劑熱經歷時酸價會上升，成形時會有搪塑成形用氯乙烯 系樹脂糊之熱安定性（溶膠黏度或觸變性等）的問題。 【專利文獻1】 特開200 1 - 207002號公報（第2頁、段 落「0005〜第3頁、段落「0011」） (三） 發明內容 本發明之目的於搪塑成形加工中，即使重複使用受到加 熱而多餘的搪塑成形用氯乙烯系樹脂糊時，該搪塑成形用 氯乙烯系樹脂糊之溶膠黏度特性或所得成形物之特性等亦 不會受到損害的搪塑成形用氯乙烯系樹脂糊，及提供使用 它所成的成形物。 本發明人等爲解決上述課題，再三深入硏究的結果發現 藉由在糊用氯乙烯系樹脂中使用可塑劑之環己烯系羧酸酯 作爲必須成分，即使重複使用於搪塑成形加工中受到加熱 、多餘的搪塑成形用氯乙烯系樹脂糊時，不會發生因熱經 歷始可塑劑之酸價上升致使溶膠黏度特性惡化的缺點情形 ，且可提高耐加熱分解性，遂而完成本發明。 換言之，本發明係提供一種搪塑成形用氯乙烯系樹脂糊 ，其特徵爲含有糊用氯乙烯系樹脂與作爲可塑劑之環己烯 系羧酸酯。 另外，本發明提供一種成形物，其特徵爲使含有糊用 氯乙烯系樹脂與作爲可塑劑之環己烯系羧酸酯之氯乙烯系 樹脂糊藉由搪塑成形法成形所得。 (四） 實施方式 於下述中更詳細說明發明。 一 8 - 1303643 本發明之搪塑成形用氯乙烯系樹脂糊係爲含有糊用氯 乙條系樹脂與作爲可塑劑之環己烯系羧酸酯所成者，在可 塑劑中該糊用氯乙烯系樹脂以分散狀態存在者。 本發明所使用的糊用氯乙烯系樹脂係爲可使用作爲可使用 於搪塑成形法之樹脂糊的氯乙烯系樹脂。該糊用氯乙烯系 - 樹脂例如聚氯乙烯樹脂、氯乙烯-醋酸乙烯酯共聚合樹脂、 氯乙燒-硬脂酸乙燃酯共聚合樹脂、氯乙嫌-乙嫌共聚合樹 脂、氯乙烯-丙烯共聚合樹脂、氯乙烯-異丁烯共聚合樹脂 、氯乙烯-甲基丙烯酸酯共聚合樹脂、氯乙烯-異丁基乙烯 φ 醚共聚合樹脂、習知單體與氯乙烯之聚氯乙烯系共聚合樹 脂、以及聚氯乙烯樹脂或聚氯乙嫌系共聚合樹脂中之氫原 子以氯原子取代的氯化聚氯乙烯系樹脂等，可以爲球狀形 · 態者。此等可以單獨使用或2種以上混合物使用。 ， 此處所指的「搪塑成形」係爲使用樹脂糊成形爲中空成 形物之加工法，詳細如下所述。 本發明使用的糊用氯乙烯系樹脂之平均粒徑以數μπι以 下較佳、更佳者爲0 · 02〜2μπι。 鲁 該糊用氯乙烯系樹脂可使藉由使氯乙烯等單體混合物乳 化聚合所得的乳液、微懸浮液聚合所得的懸浮液乾燥製得 〇 上述乳化聚合一般可使用氯乙烯等含氯之乙烯單體等單 體混合物、陰離子型界面活性劑之月桂基硫酸鈉、二辛基 磺基琥珀酸鈉等之乳化劑、及過硫酸銨、過硫酸鉀等之水 溶性觸媒，且在水介質中進行。而且，在單體中導入親水 一 9- 1303643 性基，在不使用乳化劑下進行無鹼乳化聚合。 此外，微懸浮聚合通常可使用氯乙烯等之含氯乙烯單體 等之單體混合物、陰離子型界面活性劑之月桂基硫酸鈉、 二辛基磺基琥珀酸鈉等之乳化劑、分散助劑、及月桂醯基 過氧化物、二-2 -乙基己基過氧化物等之油溶性觸媒，藉由 在水介質中以均混器等予以機械切變分散於油滴中予以進 行。 上述乳液、懸浮液等之乾燥方法例如噴霧乾燥等。 本發明之搪塑成形用氯乙烯系樹脂糊中可使用環己烯系 羧酸酯作爲可塑劑，亦可倂用除環己烯系羧酸酯外之可塑 劑。 此時，使用的全部可塑劑中環己烯系羧酸酯之含量以50 〜100重量％較佳、更佳者爲70〜100重量％、最佳者爲1〇〇 重量％環己烯系羧酸酯。環己烯系羧酸酯之含量爲50〜100 重量％時，可塑劑之耐加熱分解性優異、以及溶膠黏度、耐 擴散性、非移行性、非揮發性之平衡性優異。 本發明使用的環己烯系羧酸酯例如環己烯單羧酸酯、環 己烯二羧酸二酯、環己烯三羧酸三酯、環己烯四羧酸四酯 就與糊用氯乙烯系樹脂之相溶性及非揮發性而言，於此 等中以環己烯二羧酸二酯、環己烯三羧酸三酯較佳。 環己烯二羧酸二酯例如4 -環己烯-1，2 -二羧酸二（2 -乙 基己酯）、4 -環己烯-1，2 -二羧酸二異壬酯、4 -環己烯-1，2-二羧酸二異癸酯、2 -環己烯-1，4 -二羧酸二異壬酯等。 - 10 - 1303643 此外，環己烯三羧酸三酯例如4 -環己烯-1，2，3 -三羧酸 三（2 -乙基己酯）、5 -環己烯-1，2，4 -三羧酸三異壬酯等。 而且，本發明所使用的環己烯系羧酸酯之酸價就耐擴散 性而言以0 . 2以下較佳。 此處所指的酸價係爲必須使在1克試料中所含的酸中和 的氫氧化钾之毫克數。 本發明使用的環己烯系羧酸酯例如可藉由使環己烯系羧 酸與一元醇以習知慣用方法縮合反應製得。例如使所定原 料在氮氣氣流中、攪拌下附有回流冷凝器使多餘的一元醇 回流、直至酸價爲0.5以下，較佳者在130〜250°C下持續 加熱且使生成的水連續除去，然後較佳者在230〜180 °C、 10hPa以下（更佳者在4hPa以下）之減壓條件下，除去未反 應的醇成分且視其所需予以中和後，過濾製得具有所定形 狀之可塑劑。 此處可使用的環己烯系羧酸例如環己烯單羧酸、環己嫌 二殘酸、環己烯三羧酸、環己烯四羧酸等。此等之環己烯 系殘酸中’就與其酯化物之糊用氯乙烯系樹脂的相溶性及 非揮發性而言以環己烯二羧酸、環己烯三羧酸較佳。 上述之環己烯系二羧酸例如b環己烯_丨，2 -二羧酸、2-環己條-1,2 -二羧酸、3_環己烯- i，2_二羧酸、仁環己烯-丨，2_ 二殘酸、4 -甲基-4-環己烯_丨，2_二羧酸、丨_環己烯-13 -二 殘酸、3-環己烯-1，3-二羧酸、4_環己烯_丨，3-二羧酸、1-環己嫌-1，4 -二羧酸、2-環己烯- i，4_二羧酸等。 上述環己燒系三羧酸例如^環己烯-丨，〗，％三羧酸、3- - 11 - 1303643 環己烯-1，2,3·三羧酸、4 -環己烯-1，2,3-三羧酸、1-環己 烯-1，2,4-三羧酸、2-環己烯-1，2,4-三羧酸、3-環己烯-1，2, 4-三羧酸、4-環己烯-1，2,4-三羧酸、5-環己烯-1，2 ΜΕ殘酸、 6-環己燃 -1，2, 4-三 殘酸、 1-環己嫌 -1,3, 5-三殘 酸等。 除上述環己烯系羧酸外，可使用此等之酸酐或此等之酸 氯化物等酯形成形衍生物取代環己烯系羧酸。另外，亦可 使用此等環己烯系羧酸之烷酯化合物。該烷酯化合物中， 就脫醇反應步驟在緩和條件下進行而言以低級烷酯化合物 較佳、更佳者爲甲酯化合物。 此等可以單獨使用或2種以上混合使用。 製造本發明使用的環己烯系羧酸酯可使用的一元醇例如 丁醇、異丁醇、己醇、異己醇、庚醇、異庚醇、辛醇、異 辛醇、2 -乙基己醇、壬醇、異壬醇、2 -甲基辛醇、癸醇、 異癸醇、十一烷醇、十二烷醇、十三烷醇等。 此等可以單獨使用或2種以上混合使用。 此等之醇係使與上述環己烯系羧酸縮合反應所得的環己 烯系羧酸酯中構成醇單位者。 上述醇以具有碳數6〜11烷基之一元醇較佳。一元醇之 烷基碳數爲6〜1 1時，所得環己烯系羧酸酯之非揮發性優 異、且與糊用氯乙烯系樹脂之相溶性優異。 該具有碳數6〜11烷基之一元醇例如己醇、異己醇、庚 醇、異庚醇、辛醇、異辛醇、2 -乙基己醇、壬醇、異壬醇 、2 -甲基辛醇、癸醇、異癸醇、十一烷醇等。 -12 - 1303643 另外，上述具有烷基的碳數爲6〜11之烷基的一元醇中 ，以羥基價爲370〜420之一元醇更佳。藉由烷基之碳數爲 6〜1 1、且羥基價爲3 70〜420之一元醇例如上述一元醇中 之壬醇、異壬醇、2 -甲基辛醇等。使用同時滿足該烷基之 碳數及羥基價範圍的一元醇所得的環己烯系羧酸酯時，非 揮發性及與糊用氯乙烯系樹脂之相溶性優異。 此處所指的「羥基價」係爲使1克試料以規定方法爲基 準使用乙醯基化劑，在規定溫度及時間中反應時生成的醋 酸中和所需的氫氧化鉀之毫克數。 在爲使本發明使用的環己烯系羧酸酯合成之縮合反應時 ’爲促進縮合反應時以使用觸媒較佳。該觸媒例如對甲苯 磺酸、磷酸等之酸觸媒、四異丙基酞酸酯、四丁基酞酸酯 、二丁基錫氧化物、二辛基錫氧化物、氯化鋅等之金屬觸 媒等。 另外，於縮合反應時之溫度以1 0 0〜2 5 0 °C較佳、更佳 者爲130〜250°C。 本發明之搪塑成形用氣化乙燦系樹脂糊中可使用環己燦 系羧酸酯外之習知可塑劑。例如酞酸酯類、己二酸酯類、 癸二酸酯類、偏苯三酸酯類、均苯四甲酸酯類、環氧化大 豆油等環氧系酯類、氯化鏈烷烴類、磷酸酯類、聚酯類、 環己烷系羧酸酯等。 本發明搪塑成形用氯乙烯系樹脂糊中可塑劑之使用量， 對100重量份糊用氯乙烯系樹脂而言以10〜300重量份較 佳、更佳者爲20〜200重量份。搪塑成形用氯乙烯系樹脂 1303643 糊中可塑劑之使用量在上述範圍時，搪塑成形步驟之加工 黏度容易調整，不會產生擴散情形。 本發明之搪塑成形用氯乙烯系樹脂糊係使氯乙烯系樹脂 糊搪塑成形時，以藉由加熱來抑制糊用氯乙烯系樹脂脫鹽 ^ 酸反應爲目的時通常配合熱安定劑使用。 - 上述熱安定劑例如鉛系、錫系、Ba-Zn系、Ca-Zn系、Ζη-Κ 系、Zn-Na系等各種熱安定劑。該熱安定劑之配合量對1 00 重量份糊用氯乙烯系樹脂而言以0 . 1〜1 0重量份較佳。 本發明搪塑成形用氯乙烯系樹脂糊在不會阻害本發明目 φ 的之範圍內，可另外配合各種添加劑。該添加劑例如抗氧 化劑、紫外線吸收劑、塡充劑、稀釋劑、發泡劑、安定化 助劑等。 · 上述抗氧化劑例如2,6 -二·第3 -丁基-P-甲酚等之苯酚 - 系抗氧化劑、十八烷基-3 - ( 3，5 -二-第3 - 丁基-4 -羥基苯基） 丙酸酯等之受阻苯酚系抗氧化劑、二月桂基硫化丙酸酯等 之硫醚系抗氧化劑等。該抗氧化劑之配合量對1 〇〇重量份 糊用氯乙烯系樹脂而言以0.1〜10重量份較佳。 φ 上述紫外線吸收劑例如苯基水楊酸酯等之水楊酸酯系化 合物、2 -羥基-4-甲氧基二苯甲酮等之二苯甲酮系化合物、 2-(2’-羥基- 5’-第3 -丁基苯基）苯并三唑等之苯并三唑系化 合物、2 -乙基己基-2-氰基-3, 3’-二苯基丙烯酸酯等之氰基 丙烯酸酯系化合物、雙（2，2, 6，6·四甲基-4-吡喃基）癸酸酯 等之受阻胺化合物等。該紫外線吸收劑之配合量對1 〇〇重 量份糊用氯乙烯系樹脂而言以0.1〜1〇重量份較佳。 -1 4 一 1303643 上述塡充劑例如碳酸鈣、黏土、滑石、二氧化矽、氫氧 化鋁、氧化鎂、碳酸鎂、矽酸鎂、矽酸鈣等。該塡充劑之 配合量對100重量份糊用氯乙烯系樹脂而言以1〜120重量 較佳。 上述稀釋劑例如2,2,4 -三甲基-1，3 -戊二醇二異丁酸酯 、或正鏈烷烴等。該稀釋劑之配合量對100重量份糊用氯 乙烯系樹脂而言以1〜50重量份較佳。 上述發泡劑例如偶氮二羧酸醯胺、p，p ’ -氧化雙苯磺醯 基噠哄爲例的有機發泡劑、碳酸氫鈉爲例的無機發泡劑等 。該發泡劑之配合量對100重量份糊用氯乙烯系樹脂而言 以0.1〜30重量份較佳。 此外，上述安定化助劑例如環氧化大豆油、環氧化亞麻 仁油、丁基環氧化硬脂酸酯等環氧化合物等。 上述安定化助劑之配合量對1 00重量份糊用乙烯系樹脂 而言以0.5〜50重量份較佳。 藉由使該糊用乙烯系樹脂與作爲可塑劑之環己烯系羧酸 酯與各種添加劑混合、攪拌，使該糊用氯乙烯系樹脂與視 其所需使用的各種添加劑等分散於該可塑劑中，可製造該 可塑劑與分散於該可塑劑中之糊用氯乙烯系樹脂所成的本 發明搪塑成形用氯乙烯系樹脂糊。 使構成上述搪塑成形用氯乙烯系樹脂糊之各成分混合· 攪拌•分散時可使用的裝置例如混練機、蝶式混合機、行 星齒輪混合機、手動式混合機、雷潰機等。 搪塑成形係爲利用使糊用氯乙烯系樹脂均勻分散於可塑 - 15- 1303643 劑之搪塑成形用氯乙烯系樹脂糊的流動性予以賦形，藉由 加熱凝膠化熔融以製得成形物的成形法。 搪塑成形所使用的糊用氯乙烯系樹脂對一般氯乙烯樹脂 之粒徑約爲ΙΟΟμηι大小而言，由於糊用氯乙烯系樹脂之粒 徑爲數μπι以下之微細球狀粒子，故搪塑成形用氯乙烯系樹 脂糊保有安定的固液分散狀態，可僅藉由熱能量製得均質 成形物。 本發明之成形物可藉由使該搪塑成形用氯乙烯系樹脂 糊搪塑成形製得者。 本發明之搪塑成形用氯乙烯系樹脂糊由於含有作爲可塑 劑之環己烯系羧酸酯，故不會因反覆加熱之熱經歷、該可 塑劑之熱分解致使酸價上升，耐加熱分解性優異，故特別 有效使用於搪塑成形。 本發明所指之「搪塑成形」通常係爲順序藉由下述步驟 (1 )〜步驟（4)之各步驟以製得成形物之成形方法。 步驟（1 );自糊桶使搪塑成形用氯乙烯系樹脂糊注入模具 內，使該模具加熱，使接觸該模具內壁面之該搪塑成形用 氯乙烯系樹脂糊凝膠化以形成凝膠化層。 步驟（2 );停止加熱且使凝膠化層以外之多餘未凝膠化的 搪塑成形用氯乙烯系樹脂糊排出，回收於糊桶中。 步驟（3 );使模具再次加熱，使凝膠化層熔融，且進行完 全凝膠化。 步驟（4 );使模具冷卻且取出成形物。 藉由順序經由上述各步驟，可製得目的之中空狀成形物 一 16- 1303643 而且，上述步驟使用的模具係爲具有內壁面具企求設計 之凹凸部等殻狀物。 步驟（1 )之模具加熱方法係爲可使模具加熱的方法即可 ，沒有特別的限制，例如藉由油浴的方法、藉由空氣加熱 爐的方法等。而且，加熱溫度通常爲可使搪塑成形用氯乙 烯系樹脂糊凝膠化的溫度即可，以120〜200 °C較佳。 步驟（1 )之凝膠化層由於經過時間愈長、厚度愈厚，故 視成形物之種類而定設定適當加熱中止時期，可調整成形 物之層厚。 步驟（2 )中回收於糊桶之未凝膠化的搪塑成形用氯乙烯 系樹脂糊可再次使用於搪塑成形之步驟（1 )，此時未凝膠化 的搪塑成形用氯乙烯系樹脂糊回收於糊桶中，可在繼後的 步驟中不計次數反覆使用。 步驟（4 )之模具的冷卻方法沒有特別的限制，例如在冷 水中進行。 本發明之成形物由於使用含有以上述本發明環己#系羧 酸酯作爲必須成分之可塑劑的搪塑成形用氯乙烯系樹脂糊 ，即使重複使用該搪塑成形用氯乙烯系樹脂糊時，不會因 熱經歷、熱分解致使可塑劑之酸價上升，通常可製得非擴 散性（可塑劑之相溶性）、非移行性、非揮發性等各種特性 之平衡性優異成形物。 本發明之成形物例如玩具、手袋、汽車部材等。 本發明之成形物於上述成形物中特別就要求創意性高而 -17- 1303643 . 言以玩具較佳。 本發明所得的玩具例如軟性乙烯基玩具之娃娃、字母商 品、作飯玩具商品、圖形形式等。 此等之玩具由於通常商品之構成上ABS系樹脂或聚苯乙 烯系樹脂等接觸或組合使用，搪塑成形用氯乙烯系樹脂糊 中之可塑劑，要求不會因接觸或組合、移行至使用的此等 樹脂（即非移形性），就該點而言本發明成形物之玩具爲優 異者。 【實施例】 其次，藉由實施例更具體地說明本發明。而且，文中 之「份」全部爲以重量基準者。 《實施例1〜4》及《比較例1〜5》 以表1及表2所示配合組成調製含有糊用氯乙烯樹脂、 可塑劑及添加物之搪塑成形用氯乙烯系樹脂糊，使用它做 成片板。有關此等搪塑成形用氯乙烯系樹脂糊、可塑劑及 成形物，評估耐加熱分解性、溶膠黏度、耐擴散性、非移 行性及非揮發性的結果如表1及表2所示。 該搪塑成形用氯乙烯系樹脂糊之調製及評估方法如下所 述。 [搪塑成形用氯乙烯系樹脂糊之調製] 以表1及表2所示配合，使用混合攪拌機[東京理化器 械（股）製、B米（譯音）起始器B-100]、以攪拌回轉數 1 1 0 0 r p m、4分is的條件下進fj混合擾泮，然後在減拜下實 施靜置3 0分鐘’調製分散有糊用氯乙烯系樹脂之搪塑成形 - 1 8 - 1303643 用氯乙烯系樹脂糊。 [片板化烘烤條件] 以實施例及比較例所得的搪塑成形用氯乙烯系樹脂糊作 爲試驗片，使用瓦納（譯音）多層烤箱（瓦納多層AG製、 LTF-ST) ’在玻璃板上以1mm厚度塗覆後，在190°C烘烤10 分鐘以作成片板。 [可塑劑之耐加熱分解性的測定方法及評估基準] 使100g實施例及比較例使用的可塑劑裝入250 cc試樣 瓶，開蓋放置、1 00°C、1 4日之條件下在乾燥機中加熱。試 樣終了後，測定可塑劑之酸價與初期酸價相比，以下述評 估基準評估。 〇：酸價小於2 X :酸價爲2以上 [溶膠黏度安定性之測定方法及評估基準] <初期溶膠黏度之測定> 實施例及比較例所得的搪塑成形用氯乙烯系樹脂糊以 BM型黏度計、以滾筒No.3、6rpm、測定溫度25°C下測定。 <溶膠黏度安定性之測定> 使上述搪塑成形用氯乙烯系樹脂糊在25 °C下、7日之條 件下靜置保管，且以與初期溶膠黏度相同的條件、以BM型 黏度計、測定溶膠黏度。 對初期溶膠黏度而言算出7日後之溶膠黏度（7日後之 溶膠黏度/初期溶膠黏度）之値，以下述評估基準爲基準評 估。 - 1 9 一 1303643 〇：小於1 . 5倍 X : 1 . 5倍以上 [耐擴散性之測定方法及評估基準] 使用上述所得片板切成5cmx 5 cm之大小者作爲試驗片 ，在70°C、相對濕度95%之條件下放置10日、20日、30 曰、及40日後，以目視觀察片板狀態，且以下述評估基準 評估。 〇：沒有擴散情形。 △:沒有擴散情形，惟表面之黏腻感增加。 X :有擴散情形。 硬化：沒有擴散情形，惟可塑劑揮發、試驗片硬化。 [非移行性之測定方法及評估基準] 使用使上述所得的片板切成2 · 5mmx 2 · 5mm大小作爲試 驗片，使用ABS樹脂板[旭化成工業（股）製、史塔衣拉克( 譯音>121 ]及HIPS樹脂（高衝擊性聚苯乙烯樹脂）板[A&M苯 乙烯（股）製、AG 102]，各在2張樹脂板中以三明治狀夾住 試驗片，在10g/cm2荷重、40°C下保持24小時後，藉由使 可塑劑移行至ABS樹脂板及HIPS樹脂板，目視觀察浸鈾狀 態，以下述評估基準評估。 〇：沒有藉由可塑劑之移行浸蝕至樹脂板。 △:雖沒有藉由可塑劑之移行浸蝕至樹脂板，惟稍有痕跡 〇 X :有藉由可塑劑之移行浸飩至樹脂板情形。 X X :有顯著藉由可塑劑之移行浸蝕至樹脂板情形。 - 20- 1303643 [非揮發性之測定方法] 使用使上述所得的片板切成 5cmx 5cm大小作爲試驗片 ，預先測定重量（a )後，加入乾燥機中、在1 00°c下乾燥1 20 小時。然後，取出片板後，再測定重量（b )、藉由下述計算 式求取重量減少率（％)。 重量減少率（％) = (a-b)/axl001303643 玖 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明A vinyl chloride resin paste for molding and a molded product obtained by using the same. More specifically, the acrylonitrile-butyl which is excellent in thermal stability during molding and the sol-viscosity of the vinyl chloride-based resin paste for molding is suitable for practical use, and is required for toys of molded articles and the like. A vinyl chloride resin paste which is excellent in non-transferability and excellent in diffusibility, such as a diene-styrene resin (ABS resin) or a polystyrene resin, and a molded article obtained by using the same. Further, the vinyl chloride resin paste for molding of the present invention is generally referred to as a "blur". (2) Prior art Conventionally, a vinyl chloride resin paste has been produced by using an aromatic carboxylic acid ester which is a plasticizer in a vinyl chloride resin for paste. The carboxylic acid ester-based plasticizer, particularly bis(2-ethylhexyl phthalate) (hereinafter referred to as DOP), has a relatively balanced physical property and is suitable for dip molding, coating forming, and slewing. Forming, spiral forming, injection molding, etc., can be used in automotive interiors such as toys, handbags, wallpapers, or bed materials, automotive relationships such as undercoats or sealing layers, steel coating or canvas coating, etc. Wide range of uses. However, in the above-mentioned phthalate-based plasticizer, there is a possibility of disturbing endocrine effects and affecting the reproduction and development of wild animals or humans (so-called environmental hormones), so that it is necessary to develop industrial kinetics to replace phthalates such as DOP. It is a plasticizer with excellent properties of 1303643 plasticizer. Therefore, for example, a citric acid-based plasticizer, such as tributyl citrate (ATBC), is used as an alternative plasticizer in some applications. However, the plasticizer itself has poor heat decomposition resistance and can be plasticized under high temperature conditions. The acid value of the agent rises. In particular, a plastic molding method in which a molding method such as a toy is used is a method in which a vinyl chloride resin paste for molding a molding is injected into a mold, and the excess vinyl chloride resin paste for ungelatinized molding is discharged. However, the temperature of the vinyl chloride resin paste for molding the plastic which is discharged at this time is usually raised by 40 to 100 ° C. Therefore, it is required to be resistant to thermal stability for repeated use. Moreover, any conventional plasticizer is insufficiently resistant to the thermal stability of repeated use. One of the reasons is that the alkyl group in the plasticizer molecule is oxidatively decomposed by heating, thereby causing an increase in the acid value of the plasticizer. The acid value of the plasticizer has a great influence on the viscosity of the vinyl chloride resin paste for molding, and it is required to have good stability in terms of workability (such as sag during melting, thickness of thickness, etc.). Therefore, it is proposed to use a technique of diisodecyl adipate (DINA) of an adipate-based plasticizer, etc., and the initial viscosity can be made low-viscosity by this technique, but it is resistant to heat decomposition. There is a problem that the migration property (for a polystyrene resin or the like) and the diffusion resistance are insufficient. In order to solve the above problems, there are various proposals. For example, a technique in which a cyclohexane-based carboxylic acid ester is used as a plasticizer has been proposed (for example, refer to Patent Document 1). However, this technology is excellent in diffusion resistance and non-migration properties (for ABS resin, polystyrene resin, etc.), but the acid value of 1303643 plasticizer will increase when it is heated. The problem of thermal stability (sol viscosity, thixotropy, etc.) of the vinyl chloride resin paste for molding. [Patent Document 1] JP-A-200-207002 (page 2, paragraph "0005 to page 3, paragraph "0011") (III) SUMMARY OF THE INVENTION The object of the present invention is to re-use even in a plastic molding process. When the vinyl chloride resin paste for the molding of the vinyl chloride resin is used for heating, the sol-viscosity characteristics of the vinyl chloride resin paste for molding and the properties of the obtained molded product are not impaired. A resin paste, and a molded product obtained by using the same. In order to solve the above problems, the inventors of the present invention have found that a cyclohexene carboxylate which is a plasticizer for use as a vinyl chloride resin for paste is an essential component, even if it is repeatedly used in a slush molding process. When the vinyl chloride resin paste for heating and excess slush molding is used, there is no disadvantage that the viscosity of the sol is deteriorated due to the increase in the acid value of the plasticizer, and the heat decomposition resistance can be improved. invention. In other words, the present invention provides a vinyl chloride resin paste for slush molding, which comprises a vinyl chloride resin for paste and a cyclohexene carboxylate as a plasticizer. Further, the present invention provides a molded article obtained by molding a vinyl chloride resin paste containing a vinyl chloride resin for paste and a cyclohexene carboxylate as a plasticizer by a slush molding method. (4) Embodiments The invention will be described in more detail below. Pp. 8 - 1303643 The vinyl chloride resin paste for molding of the present invention is a mixture of a vinyl chloride resin for paste and a cyclohexene carboxylate as a plasticizer, and the paste is chlorine in a plasticizer. The vinyl resin is present in a dispersed state. The vinyl chloride resin for paste used in the present invention is a vinyl chloride resin which can be used as a resin paste which can be used in a slush molding method. The paste is made of a vinyl chloride-resin such as a polyvinyl chloride resin, a vinyl chloride-vinyl acetate copolymer resin, a chloroethene-ethyl succinate ester copolymer resin, a chloroethylene-ethyl sulphide copolymer, a vinyl chloride - propylene copolymer resin, vinyl chloride-isobutylene copolymer resin, vinyl chloride-methacrylate copolymer resin, vinyl chloride-isobutyl ethylene φ ether copolymer resin, conventional monomer and vinyl chloride polyvinyl chloride The copolymerized resin and the chlorinated polyvinyl chloride resin in which the hydrogen atom in the polyvinyl chloride resin or the polyvinyl chloride-based copolymer resin is substituted with a chlorine atom may be in a spherical shape. These may be used singly or in combination of two or more. The "plastic molding" referred to herein is a processing method in which a resin paste is used to form a hollow shape, and the details are as follows. The average particle diameter of the vinyl chloride resin for paste used in the present invention is preferably several μm or less, more preferably 0. 02 to 2 μm. The vinyl chloride resin can be obtained by drying an emulsion obtained by emulsion polymerization of a monomer mixture such as vinyl chloride or a suspension obtained by microsuspension polymerization. The emulsion polymerization can be generally carried out using a vinyl chloride such as vinyl chloride. a monomer mixture such as a monomer, an anionic surfactant, an emulsifier such as sodium lauryl sulfate or sodium dioctylsulfosuccinate; and a water-soluble catalyst such as ammonium persulfate or potassium persulfate, and in an aqueous medium In progress. Further, a hydrophilic group of 9-1303643 was introduced into the monomer, and the alkali-free emulsion polymerization was carried out without using an emulsifier. Further, as the microsuspension polymerization, a monomer mixture such as a vinyl chloride monomer such as vinyl chloride or an emulsifier or a dispersing agent such as an anionic surfactant such as sodium lauryl sulfate or dioctylsulfosuccinate may be used. And an oil-soluble catalyst such as lauryl peroxide or di-2-ethylhexyl peroxide is carried out by mechanically shearing and dispersing it in an oil droplet by a homomixer or the like in an aqueous medium. A drying method of the above emulsion, suspension or the like is, for example, spray drying or the like. In the vinyl chloride resin paste for molding of the present invention, a cyclohexene carboxylate can be used as the plasticizer, and a plasticizer other than the cyclohexene carboxylate can be used. In this case, the content of the cyclohexene carboxylate in all the plasticizers used is preferably from 50 to 100% by weight, more preferably from 70 to 100% by weight, most preferably from 1% by weight to the cyclohexene carboxylic acid. Acid ester. When the content of the cyclohexene-based carboxylic acid ester is 50 to 100% by weight, the plasticizer is excellent in heat decomposition resistance and excellent in balance of sol viscosity, diffusion resistance, non-migration property, and non-volatile property. The cyclohexene-based carboxylic acid ester used in the present invention, such as cyclohexene monocarboxylic acid ester, cyclohexene dicarboxylic acid diester, cyclohexene tricarboxylic acid triester, cyclohexene tetracarboxylic acid tetraester, and paste Among the compatibility and non-volatility of the vinyl chloride resin, among these, cyclohexene dicarboxylic acid diester and cyclohexene tricarboxylic acid triester are preferable. a cyclohexene dicarboxylic acid diester such as 4-(cyclohexene-1,2-dicarboxylic acid bis(2-ethylhexyl), 4-cyclohexene-1,2-dicarboxylic acid diisononyl ester, 4-cyclohexene-1,2-dicarboxylic acid diisononyl ester, 2-cyclohexene-1,4-dicarboxylic acid diisononyl ester, and the like. - 10 - 1303643 Further, a cyclohexene tricarboxylic acid triester such as 4-cyclohexene-1,2,3-tricarboxylic acid tris(2-ethylhexyl), 5-cyclohexene-1,2, 4-triisodecyl tricarboxylate and the like. Further, the acid value of the cyclohexene-based carboxylic acid ester used in the present invention is preferably 0.2 or less in terms of diffusion resistance. The acid value referred to herein is the number of milligrams of potassium hydroxide which must be neutralized with the acid contained in 1 gram of the sample. The cyclohexene carboxylate used in the present invention can be obtained, for example, by condensation reaction of a cyclohexene-based carboxylic acid with a monohydric alcohol by a conventional method. For example, a predetermined raw material is supplied with a reflux condenser under a nitrogen gas stream and the excess monohydric alcohol is refluxed until the acid value is 0.5 or less. Preferably, the heating is continued at 130 to 250 ° C, and the generated water is continuously removed. Then, preferably, the unreacted alcohol component is removed under reduced pressure of 230 to 180 ° C, 10 hPa or less (more preferably, 4 hPa or less), and after neutralization as needed, it is filtered to obtain a predetermined shape. Plasticizer. A cyclohexene-based carboxylic acid such as cyclohexene monocarboxylic acid, cyclohexyl di-resin, cyclohexene tricarboxylic acid, cyclohexene tetracarboxylic acid or the like which can be used herein can be used. Among these cyclohexene-based residual acids, cyclohexene dicarboxylic acid and cyclohexenetricarboxylic acid are preferred in terms of compatibility and non-volatility with the vinyl chloride resin of the esterified ester. The above cyclohexene dicarboxylic acid such as b cyclohexene 丨, 2-dicarboxylic acid, 2-cyclohexane-1,2-dicarboxylic acid, 3-cyclohexene-i,2-dicarboxylic acid , Cyclohexene-indole, 2_ diacid, 4-methyl-4-cyclohexene 丨, 2_dicarboxylic acid, 丨_cyclohexene-13-dissid acid, 3-cyclohexene- 1,3-dicarboxylic acid, 4-cyclohexene-indole, 3-dicarboxylic acid, 1-cyclohexyl-1,4-dicarboxylic acid, 2-cyclohexene-i,4-dicarboxylic acid, etc. . The above cyclohexane tricarboxylic acid such as cyclohexene-oxime, y, tricarboxylic acid, 3- 11 -1303643 cyclohexene-1,2,3·tricarboxylic acid, 4-cyclohexene-1 , 2,3-tricarboxylic acid, 1-cyclohexene-1,2,4-tricarboxylic acid, 2-cyclohexene-1,2,4-tricarboxylic acid, 3-cyclohexene-1,2 , 4-tricarboxylic acid, 4-cyclohexene-1,2,4-tricarboxylic acid, 5-cyclohexene-1,2 hydrazine residual acid, 6-cyclohexan-1,2,4-tris Acid, 1-cyclohexan-1,3, 5-tribasic acid, etc. In addition to the above cyclohexene-based carboxylic acid, an ester-forming derivative such as an acid anhydride or an acid chloride such as these may be used in place of the cyclohexene-based carboxylic acid. Further, an alkyl ester compound of such a cyclohexene carboxylic acid can also be used. In the alkyl ester compound, the lower alcohol compound is preferably a methyl ester compound in the case where the dealcoholization step is carried out under mild conditions. These may be used alone or in combination of two or more. A monohydric alcohol which can be used in the production of the cyclohexene carboxylate used in the present invention, such as butanol, isobutanol, hexanol, isohexanol, heptanol, isoheptanol, octanol, isooctanol, 2-ethylhexyl Alcohol, decyl alcohol, isodecyl alcohol, 2-methyl octanol, decyl alcohol, isodecyl alcohol, undecyl alcohol, dodecanol, tridecyl alcohol and the like. These may be used alone or in combination of two or more. These alcohols constitute an alcohol unit in the cyclohexene carboxylate obtained by the condensation reaction with the above cyclohexene-based carboxylic acid. The above alcohol is preferably one having a carbon number of 6 to 11 alkyl groups. When the alkyl carbon number of the monohydric alcohol is 6 to 1 1, the obtained cyclohexene carboxylate is excellent in non-volatility and excellent in compatibility with the vinyl chloride resin for paste. The one having a carbon number of 6 to 11 alkyl groups such as hexanol, isohexyl alcohol, heptanol, isoheptanol, octanol, isooctanol, 2-ethylhexanol, decyl alcohol, isodecyl alcohol, 2-methyl Alkyl alcohol, decyl alcohol, isodecyl alcohol, undecyl alcohol, and the like. Further, in the above monohydric alcohol having an alkyl group having an alkyl group having 6 to 11 carbon atoms, a monohydric alcohol having a valence of 370 to 420 is more preferable. The monovalent alcohol having a carbon number of the alkyl group of 6 to 1 1 and having a hydroxyl group value of 3 70 to 420 is, for example, decyl alcohol, isodecyl alcohol or 2-methyl octanol in the above monohydric alcohol. When a cyclohexene-based carboxylic acid ester obtained by simultaneously satisfying a monohydric alcohol having a carbon number and a hydroxyl group value of the alkyl group is used, it is excellent in non-volatility and compatibility with a vinyl chloride resin for paste. The "hydroxyl price" as used herein refers to the number of milligrams of potassium hydroxide required to neutralize acetic acid produced by reacting one gram of the sample with an acetylation reagent based on a predetermined method and reacting at a predetermined temperature and time. In the case of the condensation reaction for synthesizing the cyclohexene carboxylate used in the present invention, it is preferred to use a catalyst in order to promote the condensation reaction. The catalyst is a metal catalyst such as an acid catalyst such as p-toluenesulfonic acid or phosphoric acid, tetraisopropyl phthalate, tetrabutyl phthalate, dibutyltin oxide, dioctyltin oxide or zinc chloride. Media and so on. Further, the temperature at the time of the condensation reaction is preferably from 100 to 250 ° C, more preferably from 130 to 250 ° C. A conventional plasticizer other than the cyclohexyl carboxylate can be used in the vaporized ethylene resin paste for molding of the present invention. For example, phthalate esters, adipates, sebacates, trimellitates, pyromellitic esters, epoxidized soybean oils and other epoxy esters, chlorinated paraffins, phosphoric acid Esters, polyesters, cyclohexane-based carboxylic acid esters, and the like. The amount of the plasticizer used in the vinyl chloride resin paste for molding of the present invention is preferably from 10 to 300 parts by weight, more preferably from 20 to 200 parts by weight, per 100 parts by weight of the vinyl chloride resin for paste. Vinyl chloride resin for slush molding 1303643 When the amount of the plasticizer used in the paste is within the above range, the processing viscosity in the slush molding step can be easily adjusted without causing diffusion. When the vinyl chloride resin paste is molded into a vinyl chloride resin paste, the vinyl chloride resin paste of the present invention is usually used in combination with a heat stabilizer for the purpose of suppressing the desalination reaction of the vinyl chloride resin for the paste by heating. - The above-mentioned heat stabilizers are various heat stabilizers such as lead-based, tin-based, Ba-Zn-based, Ca-Zn-based, Ζη-Κ-based, and Zn-Na-based. The amount of the heat stabilizer is preferably from 0.1 to 10 parts by weight based on 100 parts by weight of the vinyl chloride resin for paste. The vinyl chloride resin paste for molding of the present invention can be blended with various additives insofar as it does not impair the object of the present invention. Such additives include, for example, an antioxidant, a UV absorber, a chelating agent, a diluent, a foaming agent, a stabilizer, and the like. · The above antioxidants such as phenol-based antioxidants such as 2,6-di-tert-butyl-P-cresol, octadecyl-3 - ( 3,5 -di- 3 -butyl-4 A thiol-based antioxidant such as a -hydroxyphenyl)propionate or a thioether-based antioxidant such as dilaurylsulfonate or the like. The amount of the antioxidant is preferably 0.1 to 10 parts by weight per 1 part by weight of the vinyl chloride resin for paste. Φ The above ultraviolet absorber is a salicylate compound such as phenyl salicylate or a benzophenone compound such as 2-hydroxy-4-methoxybenzophenone or 2-(2'-hydroxyl group). a benzotriazole-based compound such as 5'-tris-butylphenyl)benzotriazole or a cyano group such as 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate A hindered amine compound such as an acrylate compound or bis(2,2,6,6-tetramethyl-4-pyranyl) phthalate or the like. The blending amount of the ultraviolet absorber is preferably 0.1 to 1 Torr by weight based on 1 part by weight of the vinyl chloride resin for paste. -1 4 - 1303643 The above-mentioned chelating agents are, for example, calcium carbonate, clay, talc, cerium oxide, aluminum hydroxide, magnesium oxide, magnesium carbonate, magnesium citrate, calcium citrate and the like. The amount of the chelating agent is preferably from 1 to 120% by weight based on 100 parts by weight of the vinyl chloride resin for paste. The above diluent is, for example, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate or a normal paraffin. The amount of the diluent is preferably from 1 to 50 parts by weight per 100 parts by weight of the vinyl chloride resin for paste. The above-mentioned foaming agent is, for example, an organic foaming agent such as azodiamine amide, p,p'-oxydiphenylsulfonylhydrazine, or an inorganic foaming agent such as sodium hydrogencarbonate. The amount of the foaming agent is preferably 0.1 to 30 parts by weight based on 100 parts by weight of the vinyl chloride resin for paste. Further, the above-mentioned stabilization aids include epoxy compounds such as epoxidized soybean oil, epoxidized linseed oil, and butyl epoxidized stearate. The amount of the above-mentioned stabilizer is preferably from 0.5 to 50 parts by weight per 100 parts by weight of the vinyl resin for paste. By mixing and stirring the vinyl resin for the paste and the cyclohexene carboxylate as a plasticizer with various additives, the vinyl chloride resin for the paste and various additives to be used, etc., are dispersed in the plastic mold. In the agent, the vinyl chloride resin paste of the present invention which is formed of the plasticizer and the vinyl chloride resin which is dispersed in the plasticizer can be produced. The apparatus which can be used for mixing, stirring, and dispersing the components constituting the vinyl chloride resin paste for the above-mentioned slush molding, for example, a kneader, a butterfly mixer, a planetary gear mixer, a manual mixer, a thunder breaker, and the like. The slush molding is formed by forming a vinyl chloride-based resin paste for uniformly dispersing the paste vinyl chloride resin in a plastic- 15-1303643 agent, and melting it by heating gelation to obtain a shape. Forming method of matter. The vinyl chloride resin for paste used in the slush molding has a particle size of about ΙΟΟμηι for a general vinyl chloride resin, and the fine particle shape of the vinyl chloride resin for paste is several μπι or less. The vinyl chloride resin paste for molding retains a stable solid-liquid dispersion state, and a homogeneous molded product can be obtained only by thermal energy. The molded article of the present invention can be obtained by molding a vinyl chloride resin paste for molding. Since the vinyl chloride-based resin paste for molding of the present invention contains a cyclohexene-based carboxylic acid ester as a plasticizer, the thermal decomposition of the plasticizer is not caused by the thermal decomposition of the plasticizer, and the acid value is increased. It is excellent in properties and is therefore particularly effective for use in slush molding. The "plastic molding" referred to in the present invention is generally a method of forming a molded article by sequentially performing the steps of the following steps (1) to (4). Step (1); injecting a vinyl chloride resin paste for molding a molding into a mold from a paste drum, heating the mold, and gelling the vinyl chloride resin paste for molding the inner wall surface of the mold to form a condensation. Gelatinized layer. Step (2); the heating is stopped, and the excess ungelatinized vinyl chloride resin paste for molding is not discharged, and is collected in a paste bucket. Step (3); the mold is heated again to melt the gel layer and completely gelatinize. Step (4); cooling the mold and taking out the formed product. By sequentially performing the above steps, a hollow molded article of the object can be obtained. 16-1303643 Further, the mold used in the above step is a shell having a concave-convex portion designed to have an inner wall mask. The mold heating method in the step (1) is a method of heating the mold, and is not particularly limited, and examples thereof include a method using an oil bath, a method using an air heating furnace, and the like. Further, the heating temperature is usually a temperature at which the vinyl chloride resin paste for molding the molding is gelatinized, and is preferably 120 to 200 °C. Since the gelation layer of the step (1) has a longer elapsed time and a thicker thickness, it is possible to adjust the layer thickness of the molded article by setting an appropriate heating stop timing depending on the type of the molded product. The ungelatinized vinyl chloride-based resin paste which is recovered in the paste bucket in the step (2) can be reused in the step (1) of the slush molding, and the vinyl chloride which is not gelatinized at this time is formed. The resin paste is recovered in the paste bucket and can be used repeatedly in the subsequent steps without counting. The cooling method of the mold of the step (4) is not particularly limited, and is carried out, for example, in cold water. In the molded article of the present invention, a vinyl chloride resin paste for molding a vulcanization molding containing a plasticizer containing the above-mentioned cyclohexanyl carboxylate as an essential component is used, and even when the vinyl chloride resin paste for molding is used repeatedly The acid value of the plasticizer is not increased by thermal history or thermal decomposition, and a molded article excellent in balance of various properties such as non-diffusion (compatibility of a plasticizer), non-migration property, and non-volatile property can be usually obtained. The molded article of the present invention is, for example, a toy, a handbag, an automobile part or the like. The molded article of the present invention is particularly required to be highly creative in the above-mentioned molded articles, and is preferably a toy of -17 to 1303643. The toy obtained by the present invention is, for example, a soft vinyl toy doll, a letter commodity, a cooking toy product, a graphic form, and the like. These toys are used in contact with or in combination with ABS resin or polystyrene resin in the general product. The plasticizer in the vinyl chloride resin paste for molding is not required to be contacted or combined and transferred to use. Such resins (i.e., non-metamorphic) are excellent in that point, the toy of the molded article of the present invention. [Embodiment] Next, the present invention will be more specifically described by way of examples. Moreover, the "parts" in the text are all based on weight. "Examples 1 to 4" and "Comparative Examples 1 to 5" The composition of Table 1 and Table 2 was used to prepare a vinyl chloride resin paste for molding a vinyl chloride resin, a plasticizer, and an additive. It is made into a sheet. Tables 1 and 2 show the results of evaluation of resistance to heat decomposition, sol viscosity, diffusion resistance, non-migration, and non-volatileness of the vinyl chloride resin paste, the plasticizer, and the molded article for the above-mentioned slush molding. The preparation and evaluation method of the vinyl chloride resin paste for molding the molding are as follows. [Preparation of Vinyl Chloride Resin Paste for Molding and Molding] Mixing as shown in Table 1 and Table 2, using a mixing mixer [Tokyo Physicochemical Instruments Co., Ltd., BMI (Transliteration) Starter B-100], stirring The number of revolutions is 1 1 0 0 rpm, 4 minutes is under the condition of fj mixing and scrambling, and then it is left to stand for 30 minutes under the reduction of the 'modulation dispersion of the vinyl chloride resin for the paste-forming - 1 8 - 1303643 A vinyl chloride resin paste was used. [Sheet-sheet baking conditions] The vinyl chloride-based resin paste for the molding of the moldings obtained in the examples and the comparative examples was used as a test piece, and a Wana multi-layer oven (Wanna multi-layer AG, LTF-ST) was used. After coating on a glass plate at a thickness of 1 mm, it was baked at 190 ° C for 10 minutes to form a sheet. [Measurement Method and Evaluation Criteria for Resistance to Heat Decomposition of Plasticizer] 100 g of the plasticizer used in the examples and the comparative examples was placed in a 250 cc sample vial, and the lid was placed at 1,00 ° C for 14 days. Heat in a dryer. After the end of the test, the acid value of the plasticizer was determined and compared with the initial acid value, and evaluated on the basis of the following evaluation criteria. 〇: acid value is less than 2 X : acid value is 2 or more [measurement method and evaluation criteria of sol viscosity stability] <Measurement of initial sol viscosity> Vinyl chloride resin paste for stencil molding obtained in Examples and Comparative Examples The measurement was carried out by a BM type viscometer at a roller No. 3, 6 rpm and a measurement temperature of 25 °C. <Measurement of Sol Viscosity Stability> The vinyl chloride resin paste for slush molding was allowed to stand at 25 ° C for 7 days, and the BM viscosity was the same under the conditions of the initial sol viscosity. Calculate and measure the viscosity of the sol. The sol viscosity after 7 days (the sol viscosity/initial sol viscosity after 7 days) was calculated for the initial sol viscosity, and was evaluated based on the following evaluation criteria. - 1 9 一1303643 〇: less than 1.5 times X: 1. 5 times or more [Determination method and evaluation criteria of diffusion resistance] The sheet obtained by the above-mentioned sheet was cut into 5 cm x 5 cm as a test piece at 70 °. C. After 10 days, 20 days, 30 days, and 40 days under conditions of a relative humidity of 95%, the state of the sheet was visually observed and evaluated on the basis of the following evaluation criteria. 〇: There is no diffusion. △: There is no diffusion, but the sticky feeling of the surface increases. X: There is a diffusion situation. Hardening: There is no diffusion, but the plasticizer volatilizes and the test piece hardens. [Measurement method and evaluation criteria for non-migration] The sheet obtained above was cut into a size of 2 · 5 mm × 2 · 5 mm as a test piece, and ABS resin sheet was used [Asahi Kasei Kogyo Co., Ltd., Staceyak (transliteration >;121] and HIPS resin (high-impact polystyrene resin) sheet [A&M styrene (AG), AG 102], each of which was sandwiched between two resin sheets in a sandwich shape at 10 g/cm2 After the load was kept at 40 ° C for 24 hours, the state of immersion uranium was visually observed by moving the plasticizer to the ABS resin sheet and the HIPS resin sheet, and evaluated by the following evaluation criteria. 〇: No migration by resin to the resin △: Although it has not been etched into the resin sheet by the migration of the plasticizer, there is a slight trace 〇X: there is a case where the plasticizer is dipped into the resin sheet. XX: Significantly etched by the plasticizer - 20-1303643 [Measurement method of non-volatile] The sheet obtained above was cut into a size of 5 cm x 5 cm as a test piece, and the weight (a) was measured in advance and then added to a dryer at 100 ° C. Dry for 1 20 hours. Then, remove the plate Then, the weight (b) was measured again, and the weight reduction rate (%) was obtained by the following formula: Weight reduction rate (%) = (a-b)/axl00
- 2 1 - 1303643 表1 實施例1 實施例2 實施例3 比較例1 比較例2 比較例3 氯乙烯樹脂份） 100 100 100 100 100 100 環己烯系A(份） 50 環己烯系B(份） 50 環己烯系C(份） 50 D0P(份） 50 DINA(份） 50 ATBC(份） 50 環氧化大豆油*2(份） 5 、 5 5 5 5 5 Ca/Zn系安定劑*3(份） 3 3 3 3 3 3 可塑劑之耐加熱分解性 分解性 初期 0.11 0.03 0.15 0.03 0.08 0.10 14日後 0.71 0.50 0.85 3.15 10.15 3.75 耐加熱分解性評估 〇 〇 〇 X X X 溶膠黏度 初期 5540 6020 6660 6150 2430 4150 (25°C、mPa · s) 7 日後 5730 6230 6720 9840 5120 7310 黏度安定性評估 〇 〇 〇 X X X 耐擴散性10曰後 〇 〇 〇 〇 〇 硬化 20曰後 〇 〇 〇 〇 △ 硬化 30日後 〇 〇 〇 〇 X 硬化 40日後 〇 〇 Δ 〇 X 硬化 非移行性ABS樹脂板 〇 〇 〇 〇 〇 XX HIPS樹脂板 Δ Δ Δ Δ X X XX 非揮發性 重量減少率(％) 7.9 4.7 3.1 7.2 8.8 19.3- 2 1 - 1303643 Table 1 Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Vinyl chloride resin part) 100 100 100 100 100 100 Cyclohexene-based A (part) 50 Cyclohexene B (part) 50 cyclohexene system C (parts) 50 D0P (parts) 50 DINA (parts) 50 ATBC (parts) 50 epoxidized soybean oil * 2 (parts) 5, 5 5 5 5 5 Ca/Zn system stabilizer *3 (parts) 3 3 3 3 3 3 Plasticizer's resistance to thermal decomposition. Initial decomposition 0.11 0.03 0.15 0.03 0.08 0.10 After 14 days 0.71 0.50 0.85 3.15 10.15 3.75 Resistance to thermal decomposition evaluation 〇〇〇 XXX Sol viscosity initial 5540 6020 6660 6150 2430 4150 (25°C, mPa·s) 7 days later 5730 6230 6720 9840 5120 7310 Viscosity stability evaluation 〇〇〇 XXX resistance to diffusion 10 曰 after hardening 20 〇〇〇〇 〇〇〇〇 △ Hardening 30 After 〇〇〇〇X hardening for 40 days, 〇〇Δ 〇X hardened non-migrating ABS resin sheet 〇〇〇〇〇 XX HIPS resin sheet Δ Δ Δ Δ XX XX Non-volatile weight reduction rate (%) 7.9 4.7 3.1 7.2 8.819.3
-22- 1303643 表2 比較例4 實施例4 比較例5 氯乙烯樹脂+1)(份） 100 100 100 環己烯系（份） 50 耐加熱分解性試驗14日後環己烯系B(份） 50 耐加熱分解性試驗14日後環己烯系（份） 50 環氧化大豆油*2(份） 5 5 5 Ca/Zn系安定劑*3(份） 3 3 3 可塑劑之耐加熱分解性 酸價（mgKOH/g)初期 0.06 14曰 3.85 0.50 3.85 耐加熱分解性評估 X 溶膠黏度（25°C、mPa · s)初期 6570 5960 5580 7日後 7100 6200 6030 黏度安定性評估 〇 〇 〇 耐擴散性 10曰後 〇 〇 〇 20日後 〇 〇 〇 30日後 〇 〇 △ 40曰後 〇 〇 X 非移行性 ABS樹脂板 〇 〇 △ HIPS樹脂板 Δ Δ Δ 非揮發性 重量減少率（％) 5.2 4.5 5.9-22- 1303643 Table 2 Comparative Example 4 Example 4 Comparative Example 5 Vinyl chloride resin +1) (parts) 100 100 100 Cyclohexene system (parts) 50 Resistance to heat decomposition test 14 days after cyclohexene B (parts) 50 Resistance to heat decomposition test 14 days after cyclohexene system (parts) 50 epoxidized soybean oil * 2 (parts) 5 5 5 Ca / Zn system stabilizer * 3 (parts) 3 3 3 plasticizer resistant to heat-decomposable acid Price (mgKOH/g) initial 0.06 14曰3.85 0.50 3.85 Heat decomposition resistance evaluation X Sol viscosity (25 ° C, mPa · s) initial 6570 5960 5580 7 days later 7100 6200 6030 Viscosity stability evaluation 〇〇〇 diffusion resistance 10 After 20 days, after 30 days, after 〇〇〇 40曰, 〇〇X non-transition ABS resin plate 〇〇 △ HIPS resin plate Δ Δ Δ non-volatile weight reduction rate (%) 5.2 4.5 5.9
實施例4及比較例5中係使用耐加熱分解性試驗開始1 4 曰後之可塑劑，進行表2記載的評估項目。 [表1及表2記載的可塑劑說明及註解] -23- 1303643 環己烯系A:由4 -環己烯-1，2 -羧酸與2 -乙基己醇（羥 基價4 3 2 )所成的4 -環己烯-1，2 -二羧酸二（2 -乙基己酯）。 黏度 37mPa · s(25°C )。 環己烯系B:由4 -環己烯-1，2 -二羧酸與壬醇（協合發酵 (股）製、商品名；歐奇索克魯（譯音）9〇〇、羥基價3 90 )所 成的4-環己烯1，2-二羧酸二異壬酯。黏度48mPa*s(25°C) 〇 環己烯系C: 4-環己烯-1，2-二羧酸與異癸醇（羥基價355) 所成的4-環己烯-1，2-二羧酸二異癸酯。黏度67mPa · s( 2 5 〇C )。 DOP :酞酸雙（2 -乙基己酯） DINA :己二酸二異壬酯 ATBC :乙醯基檸檬酸三丁酯 環己烯系：使環己烷-1，2 -二羧酸與異壬醇（協合發酵（ 股）製、商品名；歐奇索克魯（譯音）9 00 )縮合反應的環己烯-1，2-二羧酸二異壬酯。黏度42mPa · s(25°C ) *1):糊用聚氯乙烯樹脂（聚合度1650)In Example 4 and Comparative Example 5, the evaluation items described in Table 2 were carried out using a plasticizer after the start of the heat decomposition resistance test. [Description and Notes of Plasticizers in Tables 1 and 2] -23- 1303643 Cyclohexene A: From 4-cyclohexene-1,2-carboxylic acid and 2-ethylhexanol (hydroxyl price 4 3 2 The resulting 4-(cyclohexene-1,2-dicarboxylic acid bis(2-ethylhexyl). Viscosity 37mPa · s (25 ° C). Cyclohexene B: from 4-cyclohexene-1,2-dicarboxylic acid and decyl alcohol (made by Synthetic Fermentation), trade name; Ouchi Sokolu (transliteration) 9 〇〇, hydroxyl price 3 90) The resulting dicyclodecyl 4-cyclohexene 1,2-dicarboxylate. Viscosity 48mPa*s (25°C) 〇cyclohexene C: 4-cyclohexene-1,2-dicarboxylic acid and isodecyl alcohol (hydroxyl 355) 4-cyclohexene-1,2 - Diisononyl dicarboxylate. Viscosity 67mPa · s ( 2 5 〇C ). DOP: bis(2-ethylhexyl phthalate) DINA: diisononyl adipate ATBC: tributyl citrate cyclohexene system: cyclohexane-1,2-dicarboxylic acid Isodecyl alcohol (co-fermentation (stock), trade name; Ouchi Sokolu (trans) 9 00) condensation reaction of cyclohexene-1,2-dicarboxylic acid diisononyl ester. Viscosity 42mPa · s (25°C) *1): Polyvinyl chloride resin for paste (degree of polymerization 1650)
*2):安定化助劑、大日本油墨化學工業（股）製、W-100-EL*2): Anding Chemical Additive, Dainippon Ink Chemical Industry Co., Ltd., W-100-EL
* 3 ):熱安定劑、大日本油墨化學工業（股）製、谷雷克（ 譯音）ML-610A 由表1及表2之結果可知，本發明搪塑成形用氯乙烯系 樹脂糊，就溶膠黏度、耐擴散性、非移行性、非揮發性等 而言與D0P同等，且由於搪塑成形用氯乙烯系樹脂糊中含 1303643 有環己烯系羧酸酯，故耐加熱安定性、及溶膠之黏度安定 性優異。 其中，構成環己烯系羧酸酯之醇單位的羥基價爲3 90之 實施例2係溶膠黏度、耐擴散性、非移行性、非揮發性之 平衡性極佳者。 【發明效果】 本發明之搪塑成形用氯乙烯系樹脂糊由於含有可塑劑之環 己烯系羧酸酯作爲必須成分，與習知之搪塑成形用氯乙烯 系樹脂糊相比時，於搪塑成形步驟中即使反覆加熱使用、 仍不會因熱經歷致使引起可塑劑之烷基部分熱分解，且耐 加熱分解性優異、黏度安定性、非移行性、耐擴散性、非 揮發性優異，故極適合使用於搪塑成形用。主要可廣泛利 用於藉由搪塑成形法進行成形的玩具等之中空狀成形物。* 3): Thermal stabilizer, Dainippon Ink Chemical Industry Co., Ltd., and Gurik (transliteration) ML-610A From the results of Tables 1 and 2, it is known that the vinyl chloride resin paste for molding in the present invention is The sol viscosity, the diffusion resistance, the non-migration property, the non-volatile property, and the like are the same as those of the DOP, and since the vinyl chloride resin paste for the molding process contains 1303643 cyclohexene carboxylate, it is resistant to heat stability. And the sol has excellent viscosity stability. Among them, the alcohol unit constituting the cyclohexene carboxylate has a hydroxyl group value of 3 90. In the second embodiment, the sol viscosity, the diffusion resistance, the non-migration property, and the non-volatile balance are excellent. [Effect of the Invention] The vinyl chloride resin paste for molding of the present invention is an essential component of a cyclohexene-based carboxylate containing a plasticizer, and is compared with a conventional vinyl chloride-based resin paste for molding. In the plastic molding step, even if it is used repeatedly, it does not cause thermal decomposition of the alkyl portion of the plasticizer due to thermal history, and is excellent in heat decomposition resistance, viscosity stability, non-migration property, diffusion resistance, and nonvolatile property. Therefore, it is extremely suitable for use in molding. It is mainly used in a hollow molded product such as a toy which is formed by a slush molding method.
-25--25-