TW201619036A - 捲繞用芯及捲繞用芯之製造方法 - Google Patents
捲繞用芯及捲繞用芯之製造方法 Download PDFInfo
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- TW201619036A TW201619036A TW104128370A TW104128370A TW201619036A TW 201619036 A TW201619036 A TW 201619036A TW 104128370 A TW104128370 A TW 104128370A TW 104128370 A TW104128370 A TW 104128370A TW 201619036 A TW201619036 A TW 201619036A
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- resin
- mass
- parts
- winding core
- polylactic acid
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Abstract
本發明所提供的捲繞用芯,係輕量、且尺寸精度與長條曲撓降低性均優異。
本發明的捲繞用芯,係由含有:從苯乙烯系樹脂、聚碳酸酯、聚芳酯、聚伸苯醚及聚碸之中選擇至少一種非晶性樹脂(A)、聚乳酸(B)及無機填充材的樹脂組成物所成形捲繞用芯;其中,上述樹脂組成物係由摻合:上述非晶性樹脂(A)50~80質量份、聚乳酸樹脂(B)20~50質量份而形成(其中,非晶性樹脂(A)及聚乳酸(B)的合計係100質量份)。較佳捲繞用芯係更進一步摻合無機填充材(C)10~40質量份。
Description
本發明係關於供將薄片、薄膜、帶等捲取呈捲筒狀,並執行輸送、保管等之用的捲繞用芯。材料係含有由從苯乙烯系樹脂、聚碳酸酯、聚芳酯、聚伸苯醚及聚碸之中選擇至少一種非晶性樹脂、與聚乳酸的樹脂組成物所構成捲繞用芯及其製造方法。
自習知起,例如薄片、薄膜、帶等的捲繞用芯係使用圓筒狀等形狀的塑膠芯。
塑膠芯所使用的樹脂素材係以不飽和聚酯經利用玻璃纖維、碳纖維、芳醯胺纖維等強化的纖維強化塑膠(FRP)、ABS為主流,已知有聚乙烯(PE)、聚苯乙烯(PS)、聚丙烯(PP)、聚氯乙烯(PVC)等。
因為FRP的圓筒度優異且屬於高剛性,因而可靠度高、並可增加寬度及捲繞量,但卻有非常重、對捲取機馬達的負荷高,且在運搬‧輸送時需要較大能量的問題。
另一方面,由其他樹脂構成的塑膠芯中,因為由ABS構成的塑膠芯相較於其他樹脂之下,剛性與尺寸精度均較高,因而接著FRP之後多被採用,但近年隨製膜設備的高速化、薄片等捲取量增加的要求,ABS塑膠芯的曲撓、扁平化等變形便構成問題。
所以,要求不要像FRP塑膠芯般的笨重,且尺寸安
定性較ABS塑膠芯更優異的新穎塑膠芯。針對此項課題,例如專利文獻1有記載在捲繞用芯高強度化、捲繞大量帶狀製品之目的下,有提供捲繞用芯係由外筒部與內筒部構成,且在外筒部與內筒部之間形成由板狀肋條呈輻射狀連接形狀的捲繞用芯。
專利文獻2所記載的捲繞用芯,係為降低將片狀體捲取於芯材時所發生的頸縮及凹凸、並減輕環境負荷,而由生物分解性樹脂、與壓縮永久應變較小之生物分解性樹脂的交聯發泡體雙層結構構成。
專利文獻3所記載的複層樹脂核,係為防止樹脂核發生樹脂粉、及抑制樹脂核在夾持時出現變形,而將筒狀最內層與外層使用不同特性的ABS。
專利文獻1~3雖藉由針對不同材質的層積層、及外部形狀下工夫,企圖提升塑膠芯的特性,但就材料面而言剛性尚嫌不足,效果仍不夠。
再者,專利文獻4所記載的樹脂組成物,係由聚乳酸樹脂與芳香族聚碳酸酯樹脂摻合構成。
專利文獻1:日本專利特開2013-23290號公報
專利文獻2:日本專利特開2004-43071號公報
專利文獻3:日本專利特開2004-256277號公報
專利文獻4:國際公開第2006/030951號
本發明課題在於提供:輕量、且尺寸精度(特別係尺寸安定性)、長條時之曲撓降低性(以下簡稱「曲撓降低性」)優異的捲繞用芯。
本發明者為解決上述問題經深入鑽研,結果完成以下發明。即,本發明係由以下構成。
(1)一種捲繞用芯,係將含有:從苯乙烯系樹脂、聚碳酸酯、聚芳酯、聚伸苯醚及聚碸之中選擇至少一種非晶性樹脂(A)、聚乳酸(B)及無機填充材(C)的樹脂組成物進行成形而成者;其中,上述樹脂組成物係由摻合:上述非晶性樹脂(A)50~80質量份、聚乳酸樹脂(B)20~50質量份、及無機填充材(C)10~40質量份而形成(其中,非晶性樹脂(A)及聚乳酸(B)的合計係100質量份)。
(2)如上述捲繞用芯,其中,上述無機填充材(C)係含有滑石。
(3)如上述任一項之捲繞用芯,其中,長度[L]相對於內徑[D]的比(長度[L]/內徑[D])係2以上。
(4)一種捲繞用芯,係將含有:從苯乙烯系樹脂、聚碳酸酯、聚芳酯、聚伸苯醚及聚碸之中選擇至少一種非晶性樹脂(A)、聚乳酸(B)及無機填充材(C)的樹脂組成物進行成形而成者;其中,上述捲繞用芯的長度[L]相對於內徑[D]之比(長度[L]/內徑[D])係2以上;上述樹脂組成物係摻合:上述非晶性樹脂(A)50~80質量份、及聚乳酸樹脂
(B)20~50質量份而形成(其中,非晶性樹脂(A)及聚乳酸(B)的合計係100質量份)。
(5)如上述任一項之捲繞用芯,其中,上述樹脂組成物係更進一步摻合核殼型橡膠(D)2~10質量份。
(6)如上述任一項之捲繞用芯,其中,上述樹脂組成物係更進一步摻合甲基丙烯酸系樹脂(E)2~10質量份。
(7)如上述任一項之捲繞用芯,其中,上述非晶性樹脂(A)係以苯乙烯系樹脂(a1)或聚碳酸酯(a2)為必需。
(8)一種捲繞用芯之製造方法,係包括有:摻合:從苯乙烯系樹脂、聚碳酸酯、聚芳酯、聚伸苯醚及聚碸之中選擇至少一種非晶性樹脂(A)50~80質量份、聚乳酸樹脂(B)20~50質量份、及無機填充材(C)10~40質量份,而獲得含有非晶性樹脂(A)、聚乳酸樹脂(B)及無機填充材(C)之樹脂組成物的步驟(其中,非晶性樹脂(A)及聚乳酸(B)的合計係100質量份);以及將上述樹脂組成物施行成形而獲得捲繞用芯的步驟。
(9)一種捲繞用芯之製造方法,係包括有:摻合:從苯乙烯系樹脂、聚碳酸酯、聚芳酯、聚伸苯醚及聚碸之中選擇至少一種非晶性樹脂(A)50~80質量份、與聚乳酸樹脂(B)20~50質量份,而獲得含有非晶性樹脂(A)與聚乳酸樹脂(B)之樹脂組成物的步驟(其中,非晶性樹脂(A)及聚乳酸(B)的合計係100質量份);以及將上述樹脂組成物施行成形而獲得捲繞用芯的步驟;其中,長度[L]相對於內徑[D]的比(長度[L]/內徑[D])係2以上。
(10)如上述任一項之捲繞用芯之製造方法,其中,在獲得樹脂
組成物的步驟中,更進一步摻合核殼型橡膠(D)2~10質量份。
(11)如上述任一項之捲繞用芯之製造方法,其中,在獲得樹脂組成物的步驟中,更進一步摻合甲基丙烯酸系樹脂(E)2~10質量份。
(12)如上述任一項之捲繞用芯之製造方法,其中,上述非晶性樹脂(A)係以苯乙烯系樹脂或聚碳酸酯為必需。
(13)如上述任一項之捲繞用芯之製造方法,其中,捲繞用芯的成形方法係擠出成形。
藉由本發明可提供輕量,且尺寸安定性(特別係尺寸精度)、長條曲撓降低性均優異的捲繞用芯。
以下,針對本發明捲繞用芯進行具體說明。本發明的樹脂組成物係藉由摻合非晶性樹脂(A),而達捲繞用芯的輕量化、並提升尺寸安定性。藉由聚乳酸樹脂(B)的摻合,便提升剛性、且提升捲繞用芯的尺寸安定性。
以下,針對本發明樹脂組成物中所摻合的材料進行說明。即便摻合以下所說明各種樹脂,但通常各個樹脂仍不會轉換為其他種類的樹脂,因而所摻合的樹脂會保持原本的量含於樹脂組成物中。
本發明所謂「非晶性樹脂」係指藉由使用微分掃描熱量計(DSC)
進行的熱量測定,並沒有觀察到熔解尖峰的非晶質樹脂。若例示判定方法,利用微分掃描熱量計(DSC)(島津製作所製DSC-60),依升溫速度10℃/min、測定溫度範圍40~280℃進行測定,在溫度200℃以上區域沒有觀測到熔解尖峰(吸熱)的非晶性樹脂。本發明所使用的非晶性樹脂(A)係從苯乙烯系樹脂、聚碳酸酯、聚芳酯、聚伸苯醚及聚碸之中選擇至少一種。因為該等非晶性樹脂不會隨結晶化而收縮,因而尺寸安定性優異。
本發明可使用為非晶性樹脂(A)的苯乙烯系樹脂(a1),係由至少含有芳香族乙烯系單體之單體進行聚合而獲得的聚合體。
芳香族乙烯系單體係可例如:苯乙烯、α-甲基苯乙烯、對甲基苯乙烯、乙烯基甲苯、第三丁基苯乙烯、鄰乙基苯乙烯、鄰氯苯乙烯及鄰,對二氯苯乙烯、對胺基苯乙烯等。該等係可併用2種以上。其中,較佳係使用苯乙烯或α-甲基苯乙烯。
苯乙烯系樹脂係除前述芳香族乙烯系單體之外,尚亦可為由與能和該芳香族乙烯系單體進行共聚合之其他乙烯系單體,進行共聚合而獲得的共聚合體。藉由選擇進行共聚合的其他乙烯系單體種類,便可賦予耐藥性、耐熱性等特性。能與芳香族乙烯系單體進行共聚合的其他乙烯系單體,係可例如:丙烯腈、甲基丙烯腈、乙基丙烯腈、(甲基)丙烯酸、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸環氧丙酯、烯丙基環氧丙基醚、苯乙烯對環氧丙基醚、對環氧丙基苯乙烯(甲基)丙烯
酸-2-羥乙酯、(甲基)丙烯酸-3-羥丙酯、(甲基)丙烯酸-3-羥丙酯、(甲基)丙烯酸-2,3,4,5,6-五羥基己酯、(甲基)丙烯酸-2,3,4,5,6-五羥基己酯、(甲基)丙烯酸-2,3,4,5-四羥基戊酯、順丁烯二酸、順丁烯二酸酐、順丁烯二酸單乙酯、衣康酸、衣康酸酐、酞酸、N-甲基馬來醯亞胺、N-乙基馬來醯亞胺、N-環己基馬來醯亞胺、N-苯基馬來醯亞胺、丙烯醯胺、甲基丙烯醯胺、N-甲基丙烯醯胺、丁氧基甲基丙烯醯胺、N-丙基甲基丙烯醯胺、丙烯酸胺基乙酯、丙烯酸丙胺基乙酯、甲基丙烯酸二甲胺基乙酯、甲基丙烯酸乙胺基丙酯、甲基丙烯酸苯胺基乙酯、甲基丙烯酸環己胺基乙酯、N-乙烯基二乙胺、N-乙醯基乙烯胺、烯丙胺、甲基丙烯胺(methallylamine)、N-甲基烯丙胺、2-異丙烯基唑啉、2-乙烯基唑啉、2-丙烯醯基唑啉、2-苯乙烯基唑啉等。該等亦可併用2種以上。該等之中,特別較佳係使用丙烯腈或甲基丙烯酸甲酯。
苯乙烯系樹脂(a1)100質量%中,源自芳香族乙烯系單體的結構比例,就從成形加工性的觀點,較佳係10質量%以上、更佳係20質量%以上。又,源自芳香族乙烯系單體的結構比例較佳係100質量%以下、更佳係90質量%以下。
苯乙烯系樹脂(a1)最好在由芳香族乙烯系(共)聚合體構成的基質中,分散著橡膠質聚合體的橡膠改質苯乙烯系樹脂。藉由使用該樹脂,便可更加提升捲繞用芯的耐衝擊性等特性。此種樹脂係在橡膠質聚合體上,接枝聚合著芳香族乙烯系單體、及能與該芳香族乙烯系單體進行共聚合的其他乙烯系單體而獲得。又,較佳係可使用:由芳香族乙烯系單體、及能與該芳香族乙烯系單體進行共聚合的其他乙烯系單體,進行共聚合而獲得的乙烯系共聚合體;
以及含有由在橡膠質聚合體上,接枝聚合著芳香族乙烯系單體、及能與該芳香族乙烯系單體進行共聚合的其他乙烯系單體而獲得接枝共聚合體的橡膠改質苯乙烯系樹脂。
橡膠質聚合體係可例如:聚丁二烯、苯乙烯-丁二烯共聚合體、丙烯腈-丁二烯共聚合體、苯乙烯-丁二烯的嵌段共聚合體、丙烯酸丁酯-丁二烯共聚合體等二烯系橡膠;聚丙烯酸丁酯等丙烯酸系橡膠;聚異戊二烯、及乙烯-丙烯-二烯系三元共聚合體等。該等亦可併用2種以上。其中,較佳係使用聚丁二烯與丁二烯的共聚合體。
苯乙烯系樹脂(a1)係可例如:PS(聚苯乙烯)、HIPS(耐衝擊性聚苯乙烯)、AS(丙烯腈‧苯乙烯)樹脂、ASA(丙烯腈‧苯乙烯‧丙烯酸酯)樹脂、AES(丙烯腈‧乙烯‧苯乙烯)樹脂、ABS(丙烯腈‧丁二烯‧苯乙烯)樹脂、MAS(甲基丙烯酸甲酯‧丙烯腈‧苯乙烯)樹脂、MS(甲基丙烯酸甲酯‧苯乙烯)樹脂、MABS(甲基丙烯酸甲酯‧丙烯腈‧丁二烯‧苯乙烯)樹脂、MBS(甲基丙烯酸甲酯‧丁二烯‧苯乙烯)樹脂等。該等亦可摻合2種以上。該等之中,較佳係ABS樹脂(以下稱「a1-1」)、AS樹脂(以下稱「a1-2」)。
苯乙烯系樹脂(a1)的重量平均分子量,就從依更高水準兼顧成形性與機械強度等機械物性的觀點,較佳係5萬~30萬。此處,苯乙烯系樹脂的重量平均分子量係指利用溶劑使用四氫呋喃的凝膠滲透色層分析儀(GPC),進行測定的聚苯乙烯換算值。
苯乙烯系樹脂(a1)的製造方法並無特別的限制,可使用例如:塊狀聚合法、懸浮聚合法、乳化聚合法、塊狀-懸浮聚合法等製造方法。又,亦可將依照該等任一方法所獲得1種以上的苯
乙烯系樹脂施行熔融混練進行製造。
摻合苯乙烯系樹脂(a1)的情況,其量在非晶性樹脂(A)100質量%中,較佳係50質量%以上、更佳係60質量%以上、特佳係80質量%以上。
本發明可使用為非晶性樹脂(A)的聚碳酸酯(a2),具體係由二元以上的酚系化合物、與光氣或諸如碳酸二苯酯之類的碳酸二酯化合物,進行反應而獲得的熱可塑性樹脂。
上述二元以上的酚系化合物並無特別的限制,可舉例如下述物。
首先,二元者係可舉例如下:二羥二芳基烷烴化合物:2,2-雙(4-羥苯基)丙烷(通稱雙酚A)、雙(4-羥苯基)甲烷、雙(4-羥苯基)苯基甲烷、雙(4-羥苯基)萘基甲烷、雙(4-羥苯基)-(4-異丙基苯基)甲烷、雙(3,5-二氯-4-羥苯基)甲烷、雙(3,5-二甲基-4-羥苯基)甲烷、1,1-雙(4-羥苯基)乙烷、1-萘基-1,1-雙(4-羥苯基)乙烷、1-苯基-1,1-雙(4-羥苯基)乙烷、1,2-雙(4-羥苯基)乙烷、2-甲基-1,1-雙(4-羥苯基)丙烷、2,2-雙(3,5-二甲基-4-羥苯基)丙烷、1-乙基-1,1-雙(4-羥苯基)丙烷、2,2-雙(3,5-二氯-4-羥苯基)丙烷、2,2-雙(3,5-二溴-4-羥苯基)丙烷、2,2-雙(3-氯-4-羥苯基)丙烷、2,2-雙(3-甲基-4-羥苯基)丙烷、2,2-雙(3-氟-4-羥苯基)丙烷、1,1-雙(4-羥苯基)丁烷、2,2-雙(4-羥苯基)丁烷、1,4-雙(4-羥苯基)丁烷、2,2-雙(4-羥苯基)戊烷、4-甲基-2,2-雙(4-羥苯基)戊烷、2,2-雙(4-羥苯基)己烷、4,4-雙(4-羥苯基)庚烷、2,2-雙(4-羥苯基)壬烷、1,10-雙(4-羥
苯基)癸烷、1,1-雙(4-羥苯基)-3,3,5-三甲基環己烷、2,2-雙(4-羥苯基)-1,1,1,3,3,3-六氟丙烷等;二羥二芳基磺化合物:雙(4-羥苯基)碸、雙(3,5-二甲基-4-羥苯基)碸、雙(3-氯-4-羥苯基)碸等;二羥二芳基環烷烴化合物:1,1-雙(4-羥苯基)環己烷、1,1-雙(3,5-二氯-4-羥苯基)環己烷、1,1-雙(4-羥苯基)環癸烷等;二羥芳基醚化合物:雙(4-羥苯基)醚、雙(3,5-二甲基-4-羥苯基)醚等;二羥二芳基酮化合物:4,4'-二羥基二苯基酮、3,3',5,5'-四甲基-4,4'-二羥基二苯基酮等;二羥二芳基硫醚化合物:雙(4-羥苯基)硫醚、雙(3-甲基-4-羥苯基)硫醚、雙(3,5-二甲基-4-羥苯基)硫醚等;二羥基二苯化合物:4,4'-二羥基二苯等;二羥二芳基亞碸化合物:雙(4-羥苯基)亞碸等;二羥芳基茀化合物:9,9-雙(4-羥苯基)茀等;二羥苯化合物:氫醌、間苯二酚、甲基氫醌等;二羥基萘化合物:1,5-二羥基萘、2,6-二羥基萘等。
三元以上的酚系化合物係可在所獲得聚碳酸酯能維持熱可塑性之範圍內使用。三元以上的酚系化合物係可例示如下:2,4,4'-三羥基二苯基酮、2,2',4,4'-四羥基二苯基酮、2,4,4'-三羥基苯醚、2,2',4,4'-四羥基苯醚、2,4,4'-三羥基二苯基-2-丙烷、2,2'-雙(2,4-二羥基)丙烷、2,2',4,4'-四羥基二苯甲烷、2,4,4'-三羥基二苯甲烷、1-[α-甲基-α-(4'-二羥苯基)乙基]-3-[α',α'-雙(4"-羥苯基)乙基]苯、1-[α-甲基-α-(4'-二羥苯基)乙基]-4-[α',α'-雙(4"-羥苯基)
乙基]苯、α,α',α"-三(4-羥苯基)-1,3,5-三異丙基苯、2,6-雙(2-羥-5'-甲基苄基)-4-甲基酚、4,6-二甲基-2,4,6-三(4'-羥苯基)-2-庚烯、4,6-二甲基-2,4,6-三(4'-羥苯基)-2-庚烷、1,3,5-三(4'-羥苯基)苯、1,1,1-三(4-羥苯基)乙烷、2,2-雙[4,4-雙(4'-羥苯基)環己基]丙烷、2,6-雙(2'-羥-5'-異丙基苄基)-4-異丙基酚、雙[2-羥-3-(2'-羥-5'-甲基苄基)-5-甲基苯基]甲烷、雙[2-羥-3-(2'-羥-5'-異丙基苄基)-5-甲基苯基]甲烷、四(4-羥苯基)甲烷、三(4-羥苯基)苯基甲烷、2',4',7-三羥黃酮、2,4,4-三甲基-2',4',7-三羥黃酮、1,3-雙(2',4'-二羥苯基異丙基)苯、三(4'-羥苯基)-戊基-s-三。
該等二元以上的酚系化合物分別係可使用1種、亦可組合使用2種以上。
聚碳酸酯(a2)係除上述所說明三元以上的酚系化合物之外,尚可在不致損及本發明效果之範圍內,含有供形成分支聚碳酸酯系樹脂用的成分。上述為獲得分支聚碳酸酯系樹脂而使用,除三元以上酚系化合物之外的分支劑材料,係可例如:苯三酚、苯六甲酸、偏苯三酸、氯化偏苯三酸(trimellitic chloride)、偏苯三酸酐、沒食子酸、沒食子酸正丙酯、兒茶酸(protocatechuic acid)、均苯四甲酸、均苯四甲酸二酐、α-雷鏈酸、β-雷鏈酸、間苯二酚-醛、氯化三甲烷(trimethyl chloride)、靛紅雙(鄰甲酚)、三氯三甲烷(trimethyl trichloride)、4-氯甲醯基酞酸酐、二苯基酮四羧酸等。
本發明所使用聚碳酸酯(a2)的共聚合成分,此外尚可使用例如:己二酸、庚二酸、辛二酸、壬二酸、癸二酸、癸二羧酸等直鏈狀脂肪族二元羧酸。
本發明所使用聚碳酸酯(a2)的原料其中一部分,視需
要可在不致損及本發明效果之範圍內,使用當作聚合時之末端終止劑用的公知各種物。例如屬於一元酚系化合物的酚、對甲酚、對第三丁基酚、對第三辛基酚、對異丙苯基酚、溴酚、三溴酚、壬基酚等。
可使用為聚碳酸酯(a2)原料的碳酸二酯化合物,係可舉例如:碳酸二苯酯等碳酸二芳酯;碳酸二甲酯、碳酸二乙酯等碳酸二烷基酯。
本發明所使用聚碳酸酯(a2)的較佳具體例,係可例如:利用使雙酚A與光氣進行反應的界面縮聚法而獲得之聚碳酸酯;利用使雙酚A與碳酸二苯酯進行反應的熔融聚合法而獲得之聚碳酸酯。
當聚碳酸酯(a2)的骨架含有雙酚A骨架時,就從提升本發明捲繞用芯之尺寸安定性觀點,聚碳酸酯樹脂的酚性羥基末端量係雙酚A骨架每1mol,較佳0.5×10-2mol以上、更佳0.7×10-2mol以上、特佳0.9×10-2mol以上。雙酚A骨架每1mol的聚碳酸酯樹脂之酚性羥基末端量,係可利用1H-NMR等的測定計算出。即,在1H-NMR光譜中,在δ為1.66~1.70ppm範圍內有出現雙酚A的甲基尖峰,在δ為4.70~4.80ppm範圍內有出現酚性羥基末端的尖峰。從該等尖峰強度的比,便可求取雙酚A骨架每1mol的酚性羥基末端量。
酚性羥基末端量在上述範圍內的聚碳酸酯,係例如利用使雙酚A與碳酸二苯酯產生反應,且未使用末端終止劑的熔融聚合法等製造方法便可獲得。
具體的製造方法,係可例如:在反應容器中導入雙酚
A、碳酸二苯酯、鹼性觸媒、及為中和鹼性觸媒用的酸性化合物,使在惰性氣體環境下熔融,一邊攪拌一邊徐緩減壓‧升溫,且一邊除去所生成的酚一邊進行聚合的方法等。
本發明所使用聚碳酸酯(a2)的數量平均分子量(Mn)較佳係3,000以上、更佳係4,000以上、特佳係5,000以上。另一方面,聚碳酸酯(a2)的數量平均分子量(Mn)較佳係30,000以下、更佳係25,000以下。此處所謂「數量平均分子量(Mn)」係指將聚碳酸酯溶解於四氫呋喃中,再利用凝膠滲透色層分析儀(GPC)進行測定的PMMA換算之數量平均分子量。
摻合聚碳酸酯(a2)的情況,其量在非晶性樹脂(A)100質量%中,較佳係50質量%以上、更佳係60質量%以上、特佳係80質量%以上。
本發明可使用為非晶性樹脂(A)的聚芳酯(a3),係由芳香族二羧酸與雙酚進行反應而獲得的聚酯。
聚芳酯(a3)係可利用熔融聚合法、界面聚合法等公知方法進行製造。
能成為聚芳酯(a3)之原料的芳香族二羧酸係可舉例如:對酞酸、異酞酸、酞酸、2,5-萘二羧酸、2,6-萘二羧酸、2,7-萘二羧酸、1,5-萘二羧酸、甲基對酞酸、4,4'-聯苯基二羧酸、2,2'-聯苯基二羧酸、4,4'-聯苯醚二羧酸、4,4'-二苯甲烷二羧酸、4,4'-二苯碸二羧酸、4,4'-二苯基亞異丙基二羧酸、1,2-雙(4-羧基苯氧基)乙烷、5-間苯二甲酸磺酸鈉。其中,較佳係對酞酸、異酞酸。又,就
從樹脂組成物的熔融加工性、及所獲得捲繞用芯的機械特性觀點,更佳係二者併用。對酞酸與異酞酸的混合莫耳比率(對酞酸/異酞酸)係可在100/0~0/100範圍內任意選擇。就從界面聚合法時的聚合性觀點,對酞酸與異酞酸的混合莫耳比率(對酞酸/異酞酸)較佳係30/70以上、更佳係40/60以上。另一方面,就從界面聚合法時的聚合性觀點,對酞酸與異酞酸的混合莫耳比率(對酞酸/異酞酸)較佳係70/30以下、更佳係60/40以下。又,當考慮所獲得聚芳酯的特性時,若增加異酞酸的比率,便會有抑制聚芳酯之光變色的傾向,而若增加對酞酸的比率,便會有提升聚芳酯樹脂之耐熱性的傾向。
能成為聚芳酯(a3)其他原料的雙酚係可舉例如:2,2-雙(4-羥苯基)丙烷[另稱:雙酚A]、2-苯基-3,3-雙(4-羥苯基)苄甲內醯胺、4,4'-(3,3,5-三甲基亞環己基)二酚、2,2-雙(4-羥-3,5-二甲基苯基)丙烷、2,2-雙(4-羥-3,5-二溴苯基)丙烷、2,2-雙(4-羥-3,5-二氯苯基)丙烷、4,4'-二羥基二苯碸、4,4'-二羥基二苯醚、4,4'-二羥基二苯硫醚、4,4'-二羥基二苯基酮、4,4'-二羥基二苯甲烷、1,1-雙(4-羥苯基)環己烷。該等雙酚係可單獨使用、亦可混合使用2種以上。其中,就從聚合性及經濟性的觀點,較佳係使用2,2-雙(4-羥苯基)丙烷。又,就從耐熱性的觀點,較佳係使用2-苯基-3,3-雙(4-羥苯基)苄甲內醯胺、4,4'-(3,3,5-三甲基亞環己基)二酚。
本發明可使用為非晶性樹脂(A)的聚伸苯醚(a4)並無特別的限定。例如:聚(2,6-二甲基-1,4-伸苯基醚)、聚(2-甲基-6-乙基-1,4-伸苯基醚)、聚(2-甲基-6-苯基-1,4-伸苯基醚)、聚(2,6-二氯-1,4-伸苯基
醚)等。又,尚可例如:2,6-二甲基酚與其他酚類(例如2,3,6-三甲基酚、2-甲基-6-丁基酚)的共聚合體之類的聚伸苯醚共聚合體。其中,更佳係聚(2,6-二甲基-1,4-伸苯基醚)、2,6-二甲基酚與2,3,6-三甲基酚的共聚合體。又,特佳係聚(2,6-二甲基-1,4-伸苯基醚)。
聚烯烴氧化物(polyolefin oxide)(a4)的製造方法並無特別的限定,例如美國專利第3306874號說明書所記載方法,將亞銅鹽與胺的混合使用為觸媒,利用將例如2,6-二甲基酚進行氧化聚合而製造的方法。其他尚亦可例如美國專利第3306875號說明書、美國專利第3257357號說明書及美國專利第3257358號說明書所記載的方法。
本發明可使用為非晶性樹脂(A)的聚碸(a5),係以伸芳單元、醚鍵結(-O-)及碸鍵結(-SO2-)為必需,且伸芳單元利用醚鍵及碸鍵而位於無秩序或秩序佳位置的聚伸芳化合物。
本發明所使用的聚碸(a5)係將所對應的雙(鹵芳基)碸與雙(羥芳基)化合物,使用鹼進行脫鹵氫反應(dehydrohalogenation),藉由使進行縮聚便可製造。
再者,聚碸(a5)的市售物例係可例如:住友化學(股)製的「"SUMIKAEXCEL"(註冊商標)PES3600P」、「"SUMIKAEXCEL"(註冊商標)PES4100P」;AMOCO公司製的「"UDEL" P-1700」。另外,聚碸的末端基係可依照其製法再行適當選擇,例如鹵原子、羥基、烷氧基。
本發明的非晶性樹脂(A)較佳係苯乙烯系樹脂(a1)及/或聚碳酸酯(a2),當非晶性樹脂係使用苯乙烯系樹脂時可獲得輕量性特別優異的捲繞用芯;當非晶性樹脂係使用聚碳酸酯時可獲得尺寸安定性特別優異的捲繞用芯。所以,非晶性樹脂(A)較佳係以苯乙烯系樹脂(a1)及/或聚碳酸酯(a2)為必需。
非晶性樹脂亦可併用2種以上,例如併用苯乙烯系樹脂(a1)與聚碳酸酯(a2)時,可獲得尺寸精度與輕量性均衡佳的優異捲繞用芯,故屬較佳。此情況,在非晶性樹脂(A)100質量%中,苯乙烯系樹脂(a1)及聚碳酸酯(a2)較佳係合計摻合70質量%以上。
本發明所使用的聚乳酸樹脂(B)係以L-乳酸及/或D-乳酸為主要原料獲得的聚合體,但在不致損及本發明目的之範圍內,亦可含有乳酸以外的其他共聚合成分。該其他的共聚合成分單元係可例如:多元羧酸、多元醇、羥羧酸、內酯等,具體係可使用例如:草酸、丙二酸、琥珀酸、戊二酸、己二酸、壬二酸、癸二酸、十二烷二酮酸、反丁烯二酸、環己烷二羧酸、對酞酸、異酞酸、酞酸、2,6-萘二羧酸、5-間苯二甲酸磺酸鈉、5-四丁鏻磺基異酞酸等多元羧酸類;乙二醇、丙二醇、丁二醇、庚二醇、己二醇、辛二醇、壬二醇、癸二醇、1,4-環己烷二甲醇、新戊二醇、甘油、三羥甲基丙烷、季戊四醇、雙酚A、使環氧乙烷進行加成反應於雙酚的芳香族多元醇、二乙二醇、三乙二醇、聚乙二醇、聚丙二醇、聚伸丁二醇等多元醇類;甘醇酸、3-羥丁酸、4-羥丁酸、4-羥戊酸、6-羥己酸、羥
苯甲酸等羥羧酸類;乙交酯、ε-己內酯乙交酯、ε-己內酯、β-丙內酯、δ-丁內酯、β-或γ-丁內酯、新戊內酯(pivalolactone)、δ-戊內酯等內酯類等。該等共聚合成分係可單獨使用、或使用2種以上。
本發明所使用的聚乳酸樹脂(B)就從耐熱性的觀點,最好係原料乳酸的光學純度較高,在總乳酸成分中,L體或D體較佳係含有80莫耳%以上、更佳係含有90莫耳%以上、特佳係含有95莫耳%以上。在總乳酸成分中,L體或D體的上限係100莫耳%,較佳係99.9%莫耳以下、更佳係99.5莫耳%以下、特佳係98莫耳%以下。
再者,就從長條曲撓降低性的觀點,使用聚乳酸立體混合物亦屬較佳態樣之一。形成聚乳酸立體混合物的方法係可例如:將L體90莫耳%以上(較佳95莫耳%以上、更佳98莫耳%以上)的聚-L-乳酸、與D體90莫耳%以上(較佳95莫耳%以上、更佳98莫耳%以上)的聚-D-乳酸,利用熔融混練或溶液混練等進行混合的方法。又,其他方法尚亦可例如由聚-L-乳酸與聚-D-乳酸形成嵌段共聚合體的方法。就從較容易形成聚乳酸立體混合物的觀點,最好係將L-乳酸與D-乳酸進行嵌段共聚合的方法。
本發明所使用聚乳酸樹脂(B)的製造方法係可使用已知的聚合方法,可採用由乳酸進行的直接聚合法、經由交酯進行的開環聚合法等。
本發明所使用聚乳酸樹脂(B)的分子量與分子量分佈,係在實質能成形加工之前提下,其餘並無特別的限定,就重量平均分子量較佳係10,000以上、更佳係40,000以上、特佳係80,000
以上。此處所謂「重量平均分子量」係指利用溶劑使用六氟異丙醇的凝膠滲透色層分析儀(GPC)進行測定,聚甲基丙烯酸甲酯(PMMA)換算的重量平均分子量。
本發明所使用聚乳酸樹脂(B)的熔點並無特別的限定,較佳係90℃以上、更佳係150℃以上。
成為本發明捲繞用芯材料的樹脂組成物,相對於前所列舉非晶性樹脂(A)與聚乳酸樹脂(B)的合計100質量份,摻合非晶性樹脂(A)50~80質量份、及聚乳酸樹脂(B)20~50質量份。藉由將非晶性樹脂(A)及聚乳酸樹脂(B)的摻合量設定在上述範圍內,便可獲得強度與韌性的均衡優異之樹脂組成物,由其成形獲得的捲繞用芯屬於輕量,且尺寸安定性優異。就從更加提升長條曲撓降低性與尺寸安定性的觀點,較佳係摻合非晶性樹脂(A)55質量份以上、聚乳酸樹脂(B)45質量份以下,就從更加提升輕量性的觀點,更佳係摻合非晶性樹脂(A)57質量份以上、聚乳酸樹脂(B)43質量份以下。另一方面,就從更加提升長條曲撓降低性與尺寸安定性的觀點,較佳係摻合非晶性樹脂(A)70質量份以下、聚乳酸樹脂(B)30質量份以上,就從更加提升輕量性均衡的觀點,更佳係摻合非晶性樹脂(A)65質量份以下、聚乳酸樹脂(B)35質量份以上。
再者,當非晶性樹脂(A)係以苯乙烯系樹脂(a1)及聚碳酸酯(a2)為必需的情況,在非晶性樹脂(A)100質量%中,苯乙烯系樹脂(a1)及聚碳酸酯(a2)最好合計摻合70質量%以上。
本發明中,可在樹脂組成物中摻合核殼型橡膠(D)。藉由摻合核殼型橡膠(D),便可提升本發明捲繞用芯的圓筒度,更可賦予耐衝擊性,故屬較佳。
本發明的核殼型橡膠(D)係內部以橡膠為原料的核部,且外部具有殼層的粒子狀聚合體,內部與外部係不同的組成,使乙烯系單體進行接枝聚合於橡膠者。在核部與最外的殼層之間亦可設有其他層。
核殼型橡膠(D)中,就核部的橡膠種類並無特別的限定,只要由具橡膠彈性之聚合體成分構成者便可。例如:使丙烯酸成分、聚矽氧成分、腈成分、共軛二烯成分、胺酯成分或乙烯丙烯成分等進行聚合而獲得的橡膠。較佳橡膠係例如使丙烯酸乙酯單元、丙烯酸丁酯單元等丙烯酸成分;或二甲基矽氧烷單元、苯基甲基矽氧烷單元等聚矽氧成分;或丙烯腈單元、甲基丙烯腈單元等腈成分;或丁二烯單元、異戊二烯單元等共軛二烯成分進行聚合者所構成的橡膠。又,最好由該等成分組合2種以上進行共聚合者所構成的橡膠。
橡膠的更佳具體例係如下:由丙烯酸乙酯單元、丙烯酸丁酯單元等丙烯酸成分進行聚合的成分所構成橡膠、由二甲基矽氧烷單元、苯基甲基矽氧烷單元等聚矽氧成分進行聚合的成分所構成橡膠、以及由該等的組合(即丙烯酸乙酯單元、丙烯酸丁酯單元等丙烯酸成分、及二甲基矽氧烷單元、苯基甲基矽氧烷單元等聚矽氧成分)進行共聚合的成分所構成橡膠。最佳橡膠係由丙烯酸乙酯單元、丙烯酸丁酯單元等丙烯酸成
分進行聚合的成分所構成橡膠。
核殼型橡膠中,殼層係除丙烯酸環氧丙酯或甲基丙烯酸環氧丙酯等含有環氧丙基之乙烯系單體外,尚亦可使從不飽和羧酸烷基酯系單體、不飽和二羧酸酐系單體、脂肪族乙烯系單體、氰化乙烯系單體、馬來醯亞胺系單體、不飽和二羧酸系單體、或其他乙烯系單體等之中選擇至少1種單體進行接枝聚合者。其中,較佳係使含有從不飽和羧酸烷基酯系單體或不飽和二羧酸酐系單體之中選擇至少1種的單體進行接枝聚合者。另外,當核殼型橡膠係具有源自芳香族乙烯系單體之結構,且屬於非晶質時,為求定義明確化,便歸類為上述苯乙烯系樹脂(a1)。
不飽和羧酸烷基酯系單體並無特別的限定,較佳係使用(甲基)丙烯酸烷基酯。具體係可例如:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸十八烷基酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸氯甲酯、(甲基)丙烯酸-2-氯乙酯、(甲基)丙烯酸-2-羥乙酯、(甲基)丙烯酸-3-羥丙酯、(甲基)丙烯酸-2,3,4,5,6-五羥基己酯、(甲基)丙烯酸-2,3,4,5-四羥基戊酯、丙烯酸胺基乙酯、丙烯酸丙胺基乙酯、甲基丙烯酸二甲胺基乙酯、甲基丙烯酸乙胺基丙酯、甲基丙烯酸苯胺基乙酯、或甲基丙烯酸環己胺基乙酯等,就從提升耐衝擊性的效果較大之觀點,較佳係使用(甲基)丙烯酸甲酯。該等單體係可使用1種以上。
不飽和二羧酸酐系單體係可例如:順丁烯二酸酐、衣康酸酐、戊烯二酸酐、檸康酸酐或烏頭酸酐等,就從提升耐衝擊性
的效果較大之觀點,較佳係使用順丁烯二酸酐。該等單元係可使用1種或2種以上。
再者,脂肪族乙烯系單體係可例示如:乙烯、丙烯、丁二烯等。氰化乙烯系單體係可例示如:丙烯腈、甲基丙烯腈或乙基丙烯腈(ethacrylonitrile)等。馬來醯亞胺系單元係可例示如:馬來醯亞胺、N-甲基馬來醯亞胺、N-乙基馬來醯亞胺、N-丙基馬來醯亞胺、N-異丙基馬來醯亞胺、N-環己基馬來醯亞胺、N-苯基馬來醯亞胺、N-(對溴苯基)馬來醯亞胺、N-(氯苯基)馬來醯亞胺等。不飽和二接酸系單體係可例示如:順丁烯二酸、順丁烯二酸單乙酯、衣康酸、酞酸等。其他的乙烯系單體係可舉例如:丙烯醯胺、甲基丙烯醯胺、N-甲基丙烯醯胺、丁氧基甲基丙烯醯胺、N-丙基甲基丙烯醯胺、N-乙烯基二乙胺、N-乙醯基乙烯胺、烯丙胺、甲基丙烯胺、N-甲基烯丙胺、對胺基苯乙烯、2-異丙烯基唑啉、2-乙烯基唑啉、2-丙烯醯基唑啉、或2-苯乙烯基唑啉等。可使用該等單體1種以上。
核殼型橡膠(D)的較佳具體例係可例如下述:核部為丙烯酸丁酯聚合體、且殼層為甲基丙烯酸甲酯/甲基丙烯酸環氧丙酯共聚合體者;核部為二甲基矽氧烷/丙烯酸丁酯共聚合體、且殼層為甲基丙烯酸甲酯/甲基丙烯酸環氧丙酯共聚合體者;核部為丙烯酸丁酯聚合體、且殼層為甲基丙烯酸甲酯聚合體者;核部為二甲基矽氧烷/丙烯酸丁酯共聚合體、且殼層為甲基丙烯酸甲酯聚合體者。該等之中,就從外觀改善效果明顯的觀點,較佳係核部為丙烯酸丁酯聚合體、且殼層為甲基丙烯酸甲酯/甲基丙烯酸環氧丙酯共聚合體者,核部為丙烯酸丁酯聚合體、且殼層為甲基丙烯酸甲酯
聚合體者。最佳係核部為丙烯酸丁酯聚合體、且殼層為甲基丙烯酸甲酯/甲基丙烯酸環氧丙酯共聚合體者。
核殼型橡膠(D)粒子的中數粒徑並無特別的限定,較佳係0.05μm以上、更佳係0.1μm以上、特佳係0.2μm以上。另一方面,核殼型橡膠(C)粒子的中數粒徑較佳係1μm以下、更佳係0.8μm以下、特佳係0.6μm以下。此處所謂「核殼型橡膠的中數粒徑」係指利用精密粒度分佈測定裝置(Beckman Coulter公司製Multisizer)所測定積分粒度分佈曲線的50%體積平均粒徑。具體而言,使用碰觸式攪拌機(touch mixer)及超音波,使試料0.1g預分散於0.1%非離子系界面活性劑10ml中,再將其於具主機之充滿測定用電解液的燒杯中,一邊徐緩攪拌一邊利用滴管滴下,使主機畫面的濃度計顯示度數合致於10%左右。接著,在測定裝置主機上輸入:篩孔度(aperture size)50μm、電流800、增益4、極性+,並利用手動施行測定。測定中依燒杯內不會進入氣泡的程度徐緩攪拌,在測定到核殼型橡膠10萬個的時點便結束測定。從所獲得粒度分佈計算出中數粒徑。
核殼型橡膠(D)中,核與殼的質量比並無特別的限定,相對於核殼型橡膠全體100質量份,核部較佳係50質量份以上、更佳係55質量份以上、特佳係60質量份以上。另一方面,相對於核殼型橡膠全體,核部較佳係95質量份以下、更佳係93質量份以下、特佳係90質量份以下。
核殼型橡膠(D)的摻合量,相對於上述非晶性樹脂(A)與聚乳酸樹脂(B)的合計量100質量份,較佳係2質量份以上,利用該量便可更加提升耐衝擊性。另一方面,核殼型橡膠(D)的摻合
量,相對於上述非晶性樹脂(A)與聚乳酸樹脂(B)的合計量100質量份,較佳係10質量份以下、更佳係6質量份以下。藉由將核殼型橡膠(D)的摻合量設定在10質量份以下,便可抑制因最外層所含有環氧丙基的影響而造成凝膠化,俾可更加提升捲繞用芯的表面平滑性及圓筒度。
核殼型橡膠(D)係滿足上述條件者,可使用市售物,亦可利用公知方法製作。市售物係可例如:三菱嫘縈製"METABLEN"(註冊商標)、Kaneka製"Kane-Ace"(註冊商標)、Rohm and Haas製"PARALOID"(註冊商標)、武田藥品工業製"STAPHYLOID"或KURARAY製"PARAFACE"(註冊商標)等,該等係可使用1種或2種以上。其中,最好使用核部含有丙烯酸丁酯單元、最外層含有甲基丙烯酸環氧丙酯單元的Rohm and Haas製"PARALOID EXL2314"等,惟並不僅侷限於此。
本發明中,可在樹脂組成物中更進一步摻合甲基丙烯酸系樹脂(E)。樹脂組成物中,亦可併用摻合核殼型橡膠(D)與甲基丙烯酸系樹脂(E)。
藉由在樹脂組成物中更進一步摻合甲基丙烯酸系樹脂(E),便可使非晶性樹脂(A)、聚乳酸樹脂(B)、及視需要摻合的核殼型橡膠(D)之分散狀態呈安定化,可更加提升形成捲繞用芯時的長條曲撓降低性、輕量性,故屬較佳。
所謂「甲基丙烯酸系樹脂(E)」係能由(甲基)丙烯酸及/或(甲基)丙烯酸烷基酯系單體獲得的聚合體。當甲基丙烯酸系樹脂
中,因共聚合而存在有源自芳香族乙烯系單體之結構的情況,便歸類為苯乙烯系樹脂(a1)。當甲基丙烯酸系樹脂中並沒有存在源自芳香族乙烯系單體之結構,或者由(甲基)丙烯酸及/或甲基丙烯酸烷基酯系單體對橡膠進行接枝,結果具有核殼型橡膠結構的情況,便歸類為核殼型橡膠(D)。
(甲基)丙烯酸或(甲基)丙烯酸烷基酯系單體係可舉例如:甲基丙烯酸、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁基、甲基丙烯酸環己酯、甲基丙烯酸羥乙酯、甲基丙烯酸烯丙酯等,該等係可使用1種以上。
再者,亦可使用內酯環、順丁烯二酸酐、戊二酸酐等,骨架上含有環結構的共聚合體。
本發明可使用的甲基丙烯酸系樹脂(E),較佳係以甲基丙烯酸甲酯系單體為主要原料的聚甲基丙烯酸甲酯系樹脂,更佳係源自甲基丙烯酸甲酯的單元含有達70質量%以上的聚甲基丙烯酸甲酯系樹脂,特佳係甲基丙烯酸甲酯單聚體的聚甲基丙烯酸甲酯(PMMA)樹脂。
再者,甲基丙烯酸系樹脂(E)的分子量與分子量分佈係在實質能成形加工之前提下,其餘並無特別的限定,就從成形加工性的觀點,重量平均分子量較佳係1,000以上、更佳係30,000以上。另一方面,甲基丙烯酸系樹脂(E)的重量平均分子量較佳係450,000以下、更佳係200,000以下、特佳係150,000以下。此處所謂「重量平均分子量」係指利用溶劑使用四氫呋喃的GPC進行測定,聚甲基丙烯酸甲酯(PMMA)換算的重量平均分子量。
甲基丙烯酸系樹脂(E)的摻合量,相對於上述非晶性
樹脂(A)與聚乳酸樹脂(B)的合計100質量份,較佳係2質量份以上,藉此便可更加提升尺寸安定性。另一方面,甲基丙烯酸系樹脂(E)的摻合量,相對於上述非晶性樹脂(A)與聚乳酸樹脂(B)的合計100質量份,較佳係10質量份以下、更佳係6質量份以下。藉由將甲基丙烯酸系樹脂(E)的摻合量設定在10質量份以下,便可更加提升長條曲撓降低性。又,熱變形溫度較高,並可將根據ISO75(荷重0.45MPa)所測定的耐熱性(熱變形溫度)維持於80℃以上,俾能提升實用性。
在上述非晶性樹脂(A)、聚乳酸樹脂(B)、無機填充材(C)及核殼型橡膠(D)中,更進一步摻合甲基丙烯酸系樹脂(E)的樹脂組成物,其核殼型橡膠(D)與甲基丙烯酸系樹脂(E)的合計量,相對於上述非晶性樹脂(A)與聚乳酸樹脂(B)的合計100質量份,較佳係4~20質量份,就從尺寸安定性的觀點,更佳係4~12質量份。
本發明中,在含有非晶性樹脂(A)與聚乳酸樹脂(B)的本發明樹脂組成物中,最好摻合無機填充材(C)。
藉由摻合無機填充材,便可更進一步提升剛性(長條曲撓降低性)與尺寸安定性。所以,本發明的捲繞用芯因為在捲取薄片或薄膜時因捲繞用芯旋轉造成的振動較小、且薄片或薄膜不易因凹凸而變形,因而相較於習知捲繞用芯之下,可形成更長條。又,藉由提升剛性(長條曲撓降低性),便可減少成形品的厚度,俾可達更輕量化。
無機填充材(C)的具體例係可舉例如:滑石、矽鈣石、
高嶺石、蒙脫石、雲母、合成雲母、黏土、沸石、二氧化矽、石墨、碳黑、氧化亜鉛、氧化鎂、氧化鈣、氧化鈦、硫化鈣、氮化硼、碳酸鎂、碳酸鈣、硫酸鋇、氧化鋁等,就從尺寸安定性與成形品的外觀維持觀點,較佳係滑石、矽鈣石。
成為本發明捲繞用芯材料的樹脂組成物中,無機填充材(C)的摻合量相對於上述非晶性樹脂(A)與聚乳酸樹脂(B)的合計100質量份,較佳係10質量份以上,藉由該摻合量便可提升以圓筒度為代表的尺寸安定性。另一方面,無機填充材(E)的摻合量相對於上述非晶性樹脂(A)與聚乳酸樹脂(B)的合計100質量份,較佳係40質量份以下、更佳係25質量份以下,結果可達更輕量。
本發明中,更就從提升利用抑制水解而達成耐久性的觀點,可在樹脂組成物中摻合入分子中含有碳二醯亞胺基的聚合體。含碳二醯亞胺基的聚合體矽可為已市售物,其中最好可使用日清紡製"Carbodilite"(註冊商標)LA-1等。摻合量相對於上述非晶性樹脂(A)與聚乳酸樹脂(B)的合計100質量份,較佳係0.01~10質量份範圍、更佳係0.05~5質量份範圍。
本發明中,在不致損及本發明效果之範圍內,可於樹脂組成物中摻合安定劑(抗氧化劑、紫外線吸收劑、耐候劑等)、滑劑、離型劑、難燃劑、含有染料或顏料的著色劑、抗靜電劑、發泡劑等。
本發明中,在不致損及本發明效果之範圍內,可在樹脂組成物中更進一步摻合其他的結晶性熱可塑性樹脂(例如:聚醯
胺樹脂、聚苯硫醚樹脂、聚醚醚酮樹脂、除聚乳酸樹脂(B)以外的聚酯樹脂、聚醚碸樹脂、聚縮醛樹脂、聚醯亞胺樹脂、聚醚醯亞胺樹脂、芳香族及脂肪族聚酮樹脂、氟樹脂、聚偏二氯乙烯樹脂、乙烯酯系樹脂、醋酸纖維素樹脂、聚乙烯基醇樹脂等)等中之至少1種。藉由摻合該等樹脂,便可獲得具有優異特性的成形品。
成為本發明捲繞用芯材料的樹脂組成物之製造方法並無特別的限制,例如將各原料供應給單軸或雙軸擠出機、班布瑞混合機、捏和機或輥式混練機等通常公知的熔融混合機,並加熱而施行熔融混練的方法等。溫度較佳係190~250℃。原料的混合順序並無特別的限制,亦有經摻合所有原材料之後才進行熔融混練的方法。又,尚可例如經摻合其中一部分原材料之後,再施行熔融混練,然後再更摻合其餘原材料並施行熔融混練的方法。亦有經摻合其中一部分原材料之後,再利用單軸或雙軸擠出機施行熔融混練,再使用側進料器將剩餘的原材料混合於其中的方法。該等任一方法均可使用。又,相關少量添加劑成分,當然亦可在將其他成分利用上述方法等施行混練並顆粒化之後,且在成形為捲繞用芯之前才添加進行成形。
本發明的捲繞用芯係有效使用於將薄片、薄膜、帶等捲取呈捲筒狀,並進行輸送、保管等,特別係即便長條仍不易發生曲撓、扁平變形。本發明捲繞用芯並不需要加裝肋條等俾補強強度、尺寸精
度,即便單純的圓筒形狀,仍可成為高精度的薄膜用捲繞用芯,故屬較佳。特別係使用為高精度光學薄膜用時,因為尺寸安定,因而有助於薄膜不易起皺。
就從輕量性的觀點,本發明捲繞用芯的內部係中空。又,外部中捲取對象材料的部分最好至少採取圓柱形狀。
再者,能明顯獲得本發明效果的捲繞用芯形態,較佳係捲繞用芯的長度[L]30cm~5m、外徑20mm~200mm、厚度3mm~35mm。
特別係長度[L]1~4m最能發揮長條曲撓效果,故屬較佳。又,外徑75~150mm的話便能取得輕量化效果與捲繞量的均衡,故屬較佳。又,厚度5~20mm的話,就從剛性與輕量性的觀點較容易取得均衡,故屬較佳。
能特別明顯獲得發明效果的捲繞用芯之長度[L]相對於內徑[D]的比(長度[L]/內徑[D]),較佳係2以上、更佳係5以上。本發明由熱可塑性樹脂構成的捲繞用芯係尺寸安定性優異、且不易發生曲撓、變形。
習知捲繞用芯會因長度[L]越長,則尺寸安定性越降低,因而在捲取薄片、薄膜的過程中,會有逐漸發生凸凹,導致薄片、薄膜出現變形的傾向。所以,捲繞用芯就薄片、薄膜的捲繞長度便有限制。又,長度[L]越長,則越無法承受薄片、薄膜的重量,越容易發生曲撓、變形。所以,在捲取薄片、薄膜時,為抑制振動,除無法加速捲繞用芯的旋轉速度之外,尚亦必需設定薄膜、薄片的捲繞重量上限。
本發明的捲繞用芯因為尺寸安定性優異、且不易發生
曲撓、變形,因而即便就習知捲繞用芯屬困難的長條形狀,仍可依高重量、且不會有變形、振動的捲取薄片、薄膜。藉由此項效果,例如因為可進行更長的捲取,因而除可降低捲繞用芯的更換頻度,並可增加捲取的寬度。又,因為可高速捲取,因而可提高生產速度。就從該等事項觀之,可提高薄片、薄膜的生產效率。
再者,本發明的捲繞用芯因為不易發生曲撓、變形,因而當設為與習知捲繞用芯相同長度的情況,可減少厚度,便可更加輕量化,俾可減輕運搬時的負荷。
本發明的捲繞用芯係將上述樹脂組成物,利用公知的射出成形、擠出成形、充氣成形、吹塑成形等任意方法進行成形便可獲得。本發明的樹脂組成物在使其熔融物流動,再使其於模具內冷卻固化的成形方法(例如擠出成形及射出成形)中,可獲得尺寸精度佳的成形品。特別係擠出成形時可獲得圓筒度較高的捲繞用芯。此項效果係當具有上述所說明的長度與厚度較佳值、或長度及內徑之較佳比率的形狀捲繞用芯時,會明顯顯現。
以下,例示實施例所使用原料及其製造方法等。
將聚丁二烯(重量平均粒子徑0.35μm、凝膠含有率75%)50質量份、(日本ZEON股份有限公司製"Nipol LX111A2")(固形份換
算)、油酸鉀0.5質量份、葡萄糖0.5質量份、焦磷酸一鈉0.5質量份、硫酸亞鐵0.005質量份、及去離子水120質量份裝填入聚合容器中,一邊攪拌一邊升溫至65℃。將內溫達65℃的時點設為開始聚合,歷時5小時連續滴下苯乙烯35質量份、丙烯腈15質量份、及第三(十二烷基)硫醇0.3質量份。並行歷時7小時連續滴下由異丙苯過氧化氫0.25質量份、油酸鉀2.5質量份及純水25質量份構成的水溶液,而完成反應。所獲得接枝共聚合體乳膠經利用硫酸凝固,再利用苛性鈉中和後,經洗淨、過濾、乾燥便獲得粉末狀。所獲得接枝共聚合體的接枝率係50%、甲乙酮可溶分的重量平均分子量係83,000,在DSC中沒有發現到熔解尖峰。
在容量20L、且具備擋板與Pfaudler型攪拌葉片的不銹鋼製熱壓鍋中,添加將依懸浮聚合所獲得甲基丙烯酸甲酯/丙烯醯胺共聚合體(80質量%/20質量%)0.05質量份,溶解於離子交換水165質量份的溶液,再依400rpm施行攪拌,將系統內利用氮氣取代。接著,在反應系統中一邊攪拌,一邊添加苯乙烯70質量份、丙烯腈30質量份、第三(十二烷基)硫醇0.33質量份、2,2'-偶氮雙異丁腈0.31質量份,升溫至60℃而開始聚合。經歷時30分鐘將反應溫度升溫至65℃後,再歷時120分鐘升溫至100℃。以後便依照通常方法,施行反應系統的冷卻、聚合物分離、洗淨、乾燥,而獲得珠狀聚合物。所獲得AS樹脂(a1-2)的重量平均分子量係134,000,在DSC中沒有發現到熔解尖峰。
使用帝人股份有限公司"PANLITE L-1225WX"(利用雙酚A與光氣的熔融聚合法所獲得聚碳酸酯,酚性羥基末端量係雙酚A骨架每1mol為1.0×10-2mol,數量平均分子量係19,500)。又,在DSC中沒有發現到熔解尖峰。
D體量4%、L體量96%,利用GPC測定獲得依PMMA換算的重量平均分子量為220,000的聚乳酸樹脂。
滑石(Nippon Talc股份有限公司製P-6)(E-1)。
矽鈣石(林化成股份有限公司"NYGLOS M15")。
三菱嫘縈股份有限公司"METABLEN"(註冊商標)S-2001(核殼型橡膠;核:丙烯酸丁酯/二甲基矽氧烷共聚合物、殼層:甲基丙烯酸甲酯,核/殼層=80質量份/20質量份、中數粒徑0.27μm)。
住友化學股份有限公司製"SUMIPEX"(註冊商標)MH(聚甲基丙烯酸甲酯、重量平均分子量100,000)。
熔點222℃、相對黏度(1%濃硫酸溶液中、於25℃下測定)2.70的尼龍6。
將上述各材料依表1~3所示比例施行預乾式摻合。混合物使用經設定擠筒溫度220℃(料斗下側)~250℃(吐出口側)的螺旋型雙軸擠出機(Werner&Pfleiderer公司製ZSK-57)施行熔融混練,再施行造粒而獲得顆粒。
該顆粒在經調溫於80℃的熱風乾燥機中施行3小時以上的預乾燥。然後,將該顆粒使用擠出成形機,依擠筒溫度220℃(料斗下側)~250℃(吐出口側)的條件施行擠出成形,而獲得捲繞用芯。捲繞用芯的尺寸係如後述說明。針對所獲得捲繞用芯施行以下所示評價試驗。
準備複數個不同壁厚之外徑153mm 、長度300mm的捲繞用芯。捲繞用芯利用長度300mm壓頭朝圓周方向依10mm/分施行壓縮。求取此時出現變形1mm的荷重為10kgf/300mm時的壁厚。求取該壁厚的捲繞用芯質量,相對於比較例2由ABS樹脂所構成捲繞用芯質量的比率。該值越小,表示輕量性越優異。
使用外徑153mm 、且內徑[D]141mm 、長度[L]300mm、長
度[L]/厚度(D)為2.1的捲繞用芯,將定盤上所放置具測微器之支架朝軸線方向移動,在測頭碰抵於捲繞用芯上面的狀態下,橫跨全長在各種測定平面中實施測定,將此時所讀取到最大差的1/2設為圓筒度(mm)並施行評價。數值越小則圓筒度越優異。
使用內徑[D]153mm、厚度6.5mm及長度2,500mm、長度[L]/內徑[D]為16.3的芯構件,將支點間距離設為1,000mm,在距捲繞用芯中心部500mm處施加1,000kg的錘。在捲繞用芯的上面懸掛絲線,測定絲線與捲繞用芯中心部間之間隙(曲撓)。數值越小則長條曲撓降低性越優異。
結果如表1~3所示。
如表1~3所示結果得知,實施例1~15的捲繞用芯相較於比較例1~6的捲繞用芯之下,輕量性、尺寸安定性均較優異。
實施例10~14係由非晶性樹脂與聚乳酸樹脂所構成樹脂組成物獲得的捲繞用芯。將實施例10~14的捲繞用芯,與比較例1僅由非晶性樹脂構成的捲繞用芯、比較例3僅由聚乳酸樹脂構成的捲繞用芯相比較。結果,經既定量摻合非晶性樹脂與聚乳酸樹脂的捲繞用芯,圓筒度、長條曲撓降低性均獲改良,並可提升剛性,且因為可減少捲繞用芯的厚度,因而輕量性亦優異。
實施例1~4、實施例15係由非晶性樹脂、聚乳酸樹脂及無機填充材構成的樹脂組成物所形成捲繞用芯。將實施例1~4、15的捲繞用芯,與實施例5~9的捲繞用芯相比較。結果,長條曲撓降低性更優異。
實施例7及9係由在非晶性樹脂及聚乳酸樹脂中更進一步摻合核殼型橡膠的樹脂組成物所獲得捲繞用芯,相較於實施例12之下,得知圓筒度獲更進一步改良。
實施例5及6係在非晶性樹脂、聚乳酸樹脂中更進一步摻合甲基丙烯酸系樹脂的捲繞用芯,相較於實施例13及14之下,得知輕量性與長條曲撓降低性獲更進一步改良。
實施例8係在非晶性樹脂、聚乳酸樹脂中更進一步摻合核殼型橡膠與甲基丙烯酸系樹脂的捲繞用芯,相較於實施例5、7、9及12之下,得知輕量性、圓筒度、長條曲撓降低性獲更進一步改良。
實施例4及15係在非晶性樹脂、聚乳酸樹脂中更進一步摻合無機填充材的捲繞用芯,相較於實施例12之下,得知長
條曲撓降低性獲更進一步改良。
實施例1及3係在非晶性樹脂、聚乳酸樹脂中更進一步摻合核殼型橡膠與無機填充材的捲繞用芯。該等捲繞用芯相較於實施例4及15之下,得知輕量性獲改良,相較於實施例7之下,得知長條曲撓降低性獲改良。
實施例2係由非晶性樹脂、聚乳酸樹脂、核殼型橡膠、甲基丙烯酸系樹脂、無機填充材構成的捲繞用芯,得知輕量性、尺寸安定性獲最佳改良。
所以,實施例1~15的捲繞用芯係可將長條的薄膜等進行長捲繞,因為捲繞用芯自體便屬輕量,因而對捲取所需能源、運搬所需能源的減少均具貢獻。
本發明的捲繞用芯係屬於輕量,且尺寸安定性(特別係尺寸精度)與長條曲撓降低性均優異,因而特別適用為薄片、薄膜、帶等的捲繞用芯。
Claims (13)
- 一種捲繞用芯,係將樹脂組成物進行成形而成者,該樹脂組成物含有:從苯乙烯系樹脂、聚碳酸酯、聚芳酯、聚伸苯醚及聚碸中選擇之至少一種非晶性樹脂(A);聚乳酸(B);及無機填充材(C);上述樹脂組成物係摻合上述非晶性樹脂(A)50~80質量份、聚乳酸樹脂(B)20~50質量份、及無機填充材(C)10~40質量份而成(其中,非晶性樹脂(A)及聚乳酸(B)的合計係100質量份)。
- 如請求項1之捲繞用芯,其中,上述無機填充材(C)係含有滑石。
- 如請求項1或2之捲繞用芯,其中,長度[L]相對於內徑[D]的比(長度[L]/內徑[D])係2以上。
- 一種捲繞用芯,係將樹脂組成物進行成形而成者,該樹脂組成物含有:從苯乙烯系樹脂、聚碳酸酯、聚芳酯、聚伸苯醚及聚碸中選擇之至少一種非晶性樹脂(A);聚乳酸(B);及無機填充材(C);上述捲繞用芯的長度[L]相對於內徑[D]之比(長度[L]/內徑[D])係2以上;上述樹脂組成物係摻合上述非晶性樹脂(A)50~80質量份及聚乳酸樹脂(B)20~50質量份而成(其中,非晶性樹脂(A)及聚乳酸(B)的合計係100質量份)。
- 如請求項1至4中任一項之捲繞用芯,其中,上述樹脂組成物係更進一步摻合核殼型橡膠(D)2~10質量份。
- 如請求項1至5中任一項之捲繞用芯,其中,上述樹脂組成物係更進一步摻合甲基丙烯酸系樹脂(E)2~10質量份。
- 如請求項1至6中任一項之捲繞用芯,其中,上述非晶性樹脂 (A)係以苯乙烯系樹脂(a1)或聚碳酸酯(a2)為必需。
- 一種捲繞用芯之製造方法,係包括有:獲得含有非晶性樹脂(A)、聚乳酸樹脂(B)及無機填充材(C)之樹脂組成物的步驟,該樹脂組成物係摻合從苯乙烯系樹脂、聚碳酸酯、聚芳酯、聚伸苯醚及聚碸中選擇之至少一種非晶性樹脂(A)50~80質量份;聚乳酸樹脂(B)20~50質量份;及無機填充材(C)10~40質量份而得(其中,非晶性樹脂(A)及聚乳酸(B)的合計係100質量份);以及將上述樹脂組成物施行成形而獲得捲繞用芯的步驟。
- 一種捲繞用芯之製造方法,係包括有:獲得含有非晶性樹脂(A)及聚乳酸樹脂(B)之樹脂組成物的步驟,該樹脂組成物係摻合從苯乙烯系樹脂、聚碳酸酯、聚芳酯、聚伸苯醚及聚碸中選擇之至少一種非晶性樹脂(A)50~80質量份;與聚乳酸樹脂(B)20~50質量份而得(其中,非晶性樹脂(A)及聚乳酸(B)的合計係100質量份);以及將上述樹脂組成物施行成形而獲得捲繞用芯的步驟;該捲繞用芯之長度[L]相對於內徑[D]的比(長度[L]/內徑[D])係2以上。
- 如請求項8或9之捲繞用芯之製造方法,其中,在獲得樹脂組成物的步驟中,更進一步摻合核殼型橡膠(D)2~10質量份。
- 如請求項8至10中任一項之捲繞用芯之製造方法,其中,在獲得樹脂組成物的步驟中,更進一步摻合甲基丙烯酸系樹脂(E)2~10質量份。
- 如請求項8至11中任一項之捲繞用芯之製造方法,其中,上 述非晶性樹脂(A)係以苯乙烯系樹脂或聚碳酸酯為必需。
- 如請求項8至12中任一項之捲繞用芯之製造方法,其中,成形為捲繞用芯的方法係擠出成形。
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KR (1) | KR20170048326A (zh) |
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JP2004330478A (ja) * | 2003-05-01 | 2004-11-25 | Fuji Photo Film Co Ltd | ポリ乳酸樹脂の中空成形品およびその製造方法 |
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US20170218196A1 (en) | 2017-08-03 |
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EP3187541A1 (en) | 2017-07-05 |
WO2016031861A1 (ja) | 2016-03-03 |
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