TWI849138B - 聚碳酸酯樹脂組成物及具有點狀風格之外觀之成形品 - Google Patents
聚碳酸酯樹脂組成物及具有點狀風格之外觀之成形品 Download PDFInfo
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- TWI849138B TWI849138B TW109119137A TW109119137A TWI849138B TW I849138 B TWI849138 B TW I849138B TW 109119137 A TW109119137 A TW 109119137A TW 109119137 A TW109119137 A TW 109119137A TW I849138 B TWI849138 B TW I849138B
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- 239000004431 polycarbonate resin Substances 0.000 title claims abstract description 92
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- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 0.000 claims abstract description 27
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Abstract
一種聚碳酸酯樹脂組成物,其中,相對於(A)聚碳酸酯樹脂(A成分)100重量份,含有(B)表面以包含著色劑之矽酮系黏結劑樹脂被覆之合成雲母粉(B成分)0.01~8重量份,此聚碳酸酯樹脂組成物係具有成形品外觀優良之特徵。
Description
本發明係關於聚碳酸酯樹脂組成物及具有點狀風格之外觀之成形品。更詳細而言,係關於藉由在聚碳酸酯樹脂中摻合表面以包含著色劑之矽酮系黏結劑樹脂被覆之合成雲母粉,使成形品外觀優良之聚碳酸酯樹脂組成物及具有點狀風格之優良設計性之成形品。
芳香族聚碳酸酯樹脂由於具有優良之機械特性、成形性、熱性質,故係被利用於以OA機器領域、電子電氣機器領域等為中心之各式各樣的用途中。近年來,伴隨在OA機器、家電製品等的用途中之薄型輕量化,對於耐高度衝撃、高難燃且成形外觀優良之樹脂材料之要求係漸漸提高。作為這樣的材料,於專利文獻1中,係提案出在芳香族聚碳酸酯中摻合有橡膠強化苯乙烯系樹脂、滑石及矽灰石之樹脂組成物。
另一方面,在OA機器、家電製品等的用途中,對於成為具有設計性優良之外觀之成形品之樹脂材料之要求係漸漸提高。作為這樣的材料,專利文獻2中係提案有在熱可塑性樹脂中,將表面以包含著色劑之樹脂被覆之合成雲母粉摻合並分散於其中之具有石紋調外觀之熱可塑性樹脂組成物。
然而,現狀係芳香族聚碳酸酯樹脂在維持優良之機械特性、成形性、熱性質之同時,無法獲得成形品外觀優良聚碳酸酯樹脂組成物。
[先前技術文獻]
[專利文獻]
[專利文獻1]日本特開2006-342199號公報
[專利文獻2]日本特開2009-120637號公報
[發明所欲解決之課題]
本發明之目的在於提供成形品外觀優良之聚碳酸酯樹脂組成物及具有點狀風格之外觀之成形品。
[用於解決課題之手段]
本發明人等為了解決上述課題而進行積極檢討之結果,係發現藉由成為在聚碳酸酯樹脂中含有表面以包含著色劑之矽酮系黏結劑樹脂被覆之合成雲母粉之聚碳酸酯樹脂組成物,係成為成形品外觀優良之聚碳酸酯樹脂組成物,並進一步發現由該樹脂組成物形成之成形品係具有點狀風格之外觀,進而完成本發明。
亦即,依據本發明,係可提供下述(構成1)~(構成9)。
(構成1)
一種聚碳酸酯樹脂組成物,其中,相對於(A)聚碳酸酯樹脂(A成分)100重量份,含有(B)表面以包含著色劑之矽酮系黏結劑樹脂被覆之合成雲母粉(B成分)0.01~8重量份。
(構成2)
如構成1記載之聚碳酸酯樹脂組成物,其中,B成分之合成雲母粉之平均粒子徑為100~5000μm。
(構成3)
如構成1記載之聚碳酸酯樹脂組成物,其中,相對於(A)聚碳酸酯樹脂(A成分)100重量份,含有(C)橡膠強化苯乙烯系樹脂(C成分)1~100重量份。
(構成4)
如構成1記載之聚碳酸酯樹脂組成物,其中,相對於(A)聚碳酸酯樹脂(A成分)100重量份,含有(D)合成雲母粉以外之無機充填材(D成分)1~100重量份。
(構成5)
如構成4記載之聚碳酸酯樹脂組成物,其中,D成分之無機充填材係由滑石及矽灰石所成之群所選出之至少1種無機充填劑。
(構成6)
如構成1記載之聚碳酸酯樹脂組成物,其中,相對於(A)聚碳酸酯樹脂(A成分)100重量份,含有(E)阻燃劑(E成分)1~100重量份。
(構成7)
如構成1記載之聚碳酸酯樹脂組成物,其中,相對於(A)聚碳酸酯樹脂(A成分)100重量份,含有(F)防滴落劑(F成分)0.01~10重量份。
(構成8)
如構成1記載之聚碳酸酯樹脂組成物,其中,相對於(A)聚碳酸酯樹脂(A成分)100重量份,含有(G)脫模劑(G成分)0.01~10重量份。
(構成9)
一種具有點狀風格之外觀之成形品,其係由如構成1~8中之任一項所記載之聚碳酸酯樹脂組成物所形成。
[發明效果]
本發明之聚碳酸酯樹脂組成物之成形品之外觀優良,進而由於由該樹脂組成物所形成之成形品具有設計性優良之點狀風格之外觀,故適宜作為OA機器領域、電子電氣機器領域等的外殼用材料使用,尤其適於作為行動電話或平板電腦等的殼體用途。
以下,針對本發明之詳細內容進行說明。
(A成分:聚碳酸酯樹脂)
本發明中所使用之聚碳酸酯樹脂係使二價酚與碳酸酯前驅物反應所獲得者。作為反應方法之一例,係可舉出界面聚合法、熔融酯交換法、碳酸酯預聚物之固相酯交換法,及環狀碳酸酯化合物之開環聚合法等。
作為此處所使用之二價酚之代表例,係可舉出對苯二酚、間苯二酚、4,4’-聯苯酚、1,1-雙(4-羥苯基)乙烷、2,2-雙(4-羥苯基)丙烷(通稱雙酚A)、2,2-雙(4-羥基-3-甲基苯基)丙烷、2,2-雙(4-羥苯基)丁烷、1,1-雙(4-羥苯基)-1-苯基乙烷、1,1-雙(4-羥苯基)環己烷、1,1-雙(4-羥苯基)-3,3,5-三甲基環己烷、2,2-雙(4-羥苯基)戊烷、4,4’-(p-伸苯基二亞異丙基)聯苯酚、4,4’-(m-伸苯基二亞異丙基)聯苯酚、1,1-雙(4-羥苯基)-4-異丙基環己烷、雙(4-羥苯基)氧化物、雙(4-羥苯基)硫醚、雙(4-羥苯基)亞碸、雙(4-羥苯基)碸、雙(4-羥苯基)酮、雙(4-羥苯基)酯、雙(4-羥基-3-甲基苯基)硫醚、9,9-雙(4-羥苯基)茀及9,9-雙(4-羥基-3-甲基苯基)茀等。較佳之二價酚為雙(4-羥苯基)烷烴,其中,由耐衝撃性之觀點來看,特佳為雙酚A,其係廣泛地受到使用。
作為碳酸酯前驅物,係使用羰鹵化物、碳酸二酯或鹵甲酸酯等,具體而言可舉出光氣、二苯基碳酸酯或二價酚之二鹵甲酸酯等。
在透過前述二價酚與碳酸酯前驅物之界面聚合法來製造芳香族聚碳酸酯樹脂時,亦可依據需要使用觸媒、封端劑、用以防止二價酚氧化用之抗氧化劑等。此外,本發明之芳香族聚碳酸酯樹脂係包含使三官能以上之多官能性芳香族化合物進行共聚合之分支聚碳酸酯樹脂、使芳香族或脂肪族(包含脂環式)之二官能性羧酸進行共聚合之聚酯碳酸酯樹脂、使二官能性醇(包含脂環式)進行共聚合之共聚合聚碳酸酯樹脂,以及使該種二官能性羧酸及二官能性醇共同進行共聚合之聚酯碳酸酯樹脂。此外,亦可為混合2種以上之所獲得之芳香族聚碳酸酯樹脂而得之混合物。
分支聚碳酸酯樹脂係可賦予本發明之樹脂組成物滴落防止性能等。作為該分支聚碳酸酯樹脂中所使用之三官能以上之多官能性芳香族化合物,係可舉出間苯三酚、五羥基聯苯(phlorogulcide),或4,6-二甲基-2,4,6-三(4-羥苯基)庚烯-2,2,4,6-三甲基-2,4,6-三(4-羥苯基)庚烷、1,3,5-三(4-羥苯基)苯、1,1,1-三(4-羥苯基)乙烷、1,1,1-三(3,5-二甲基-4-羥苯基)乙烷、2,6-雙(2-羥基-5-甲基苄基)-4-甲基酚、4-{4-[1,1-雙(4-羥苯基)乙基]苯}-α,α-二甲基苄基酚等的三酚、四(4-羥苯基)甲烷、雙(2,4-二羥苯基)酮、1,4-雙(4,4-二羥基三苯基甲基)苯,或偏苯三酸、均苯四酸、二苯甲酮四羧酸及此等之酸氯化物等,其中,1,1,1-三(4-羥苯基)乙烷、1,1,1-三(3,5-二甲基-4-羥苯基)乙烷係較佳,1,1,1-三(4-羥苯基)乙烷係特佳。
在分支聚碳酸酯中,由多官能性芳香族化合物所衍生出之構成單元,在由2價酚所衍生出之構成單元與由該多官能性芳香族化合物所衍生出之構成單元之合計100莫耳%中,較佳為0.01~1莫耳%,更佳為0.05~0.9莫耳%,再更佳為0.05~0.8莫耳%。
此外,尤其在熔融酯交換法之情況中,雖有產生作為副反應之分支結構單元之情況,不過就該分支結構單元量,在由2價酚所衍生出之構成單元之合計100莫耳%中,較佳為0.001~1莫耳%,更佳為0.005~0.9莫耳%,再更佳為0.01~0.8莫耳%。此外,該分支結構之比例係可藉由1H-NMR測定來算出。
脂肪族之二官能性之羧酸較佳為α,ω-二羧酸。作為脂肪族之二官能性之羧酸,較佳可舉出例如,癸二酸(癸烷二酸)、十二烷二酸、十四烷二酸、十八烷二酸、二十烷二酸等的直鏈飽和脂肪族二羧酸,以及環己烷二羧酸等的脂環族二羧酸。作為二官能性醇,更適宜為脂環族二醇,可例示出例如環己烷二甲醇、環己二醇,及三環癸烷二甲醇等。
進而,亦可使用聚碳酸酯-聚二有機矽氧烷共聚合樹脂作為聚碳酸酯樹脂(A成分)。
屬於本發明之聚碳酸酯樹脂之製造方法之界面聚合法、熔融酯交換法、碳酸酯預聚物固相酯交換法及環狀碳酸酯化合物之開環聚合法等的反應形式,係在各種文獻及專利公報等廣為周知之方法。
製造本發明之聚碳酸酯樹脂組成物時,聚碳酸酯樹脂之黏度平均分子量(M)係未受到特別限定,然而較佳為1.8×104
~4.0×104
,更佳為2.0×104
~3.5×104
,再更佳為2.2×104
~3.0×104
。黏度平均分子量未滿1.8×104
之聚碳酸酯樹脂,係有無法獲得良好的機械特性之情況。另一方面,由黏度平均分子量超過4.0×104
之聚碳酸酯樹脂獲得之樹脂組成物,係由於射出成形時之流動性不良使其通用性不佳。
本發明中所謂黏度平均分子量,係首先利用奧氏黏度計,由20℃下在二氯甲烷100ml中溶解聚碳酸酯0.7g而得到的溶液求出以下述公式算出之比黏度(ηSP
)
比黏度(ηSP
)=(t-t0
)/t0
[t0
為二氯甲烷之落下秒數,t為試料溶液之落下秒數]
由求得之比黏度(ηSP
)利用下述數學式而算出黏度平均分子量M。
ηSP
/c=[η]+0.45×[η]2
c(惟[η]為極限黏度)
[η]=1.23×10-4
M0.83
c=0.7
此外,本發明之聚碳酸酯樹脂組成物中,聚碳酸酯樹脂之黏度平均分子量之計算係以下述之要點來進行。亦即,將該組成物與其20~30倍重量之二氯甲烷混合,使組成物中之可溶成分溶解。利用矽鈣石過濾來採集該可溶成分。隨後去除所得到之溶液中之溶媒。充分乾燥去除溶媒後之固體,獲得溶於二氯甲烷之成分之固體。與上述同樣地由將該固體0.7g溶於二氯甲烷100ml中所獲得之溶液求出20℃之比黏度,並與上述同樣地由該比黏度求出黏度平均分子量M。
(B成分:表面以包含著色劑之矽酮系黏結劑樹脂被覆之合成雲母粉)
本發明中所使用之合成雲母粉係表面被覆包含著色劑之矽酮系黏結劑樹脂者。
藉由使用表面被覆矽酮系黏結劑樹脂之合成雲母粉,與例如使用表面被覆環氧系黏結劑樹脂之合成雲母粉之情況相比之下,由於其黃變受到抑制故色調係優良,且可獲得良好的具有點狀風格之外觀之成形品。
作為著色劑,可舉出無機顏料、有機染顏料,若為可著色者則無特別限制。
作為無機顏料,例如,可舉出碳黑、氧化鈦、氧化物、氧化鐵、氧化鉻、銻粉、鈦黃、鋅-鐵系棕、銅-鉻系黑、銅-鐵系黑等的氧化物系顏料。
作為有機顏料或有機染料等的有機染顏料,例如可舉出酞青系染顏料;偶氮系、硫靛系、苝酮系、苝系、喹吖啶酮系、二噁嗪系、異吲哚啉酮系、喹酞酮系等的縮合多環染顏料;蒽醌系、苝酮系、苝系、次甲基系、喹啉系、雜環系、甲基系之染顏料等。此等著色劑係可單獨使用1種,亦可將2種以上混合使用。
表面被覆矽酮系黏結劑樹脂之合成雲母粉之平均粒子徑較佳為100~5000μm,更佳為200~3000μm,再更佳為300~2000μm,特佳為400~1500μm。在上述範圍內,合成雲母粉係均勻地分散於樹脂組成物中,並可獲得良好的具有點狀風格之外觀之成形品。此外,平均粒子徑係藉由Microtrac雷射繞射法來進行測定。
相對於(A)聚碳酸酯樹脂(A成分)100重量份,(B)表面以包含著色劑之矽酮系黏結劑樹脂被覆之合成雲母粉(B成分)之含量為0.01~8重量份,0.1~6重量份係較佳,0.3~5重量份係更佳,0.5~4重量份係再更佳。未達下限則無法獲得點狀風格之外觀,若超過上限則色調及外觀係惡化。
本發明之聚碳酸酯樹脂組成物係可提供進一步含有各種染顏料並表現多樣的設計性之成形品。藉由摻合螢光增白劑或其以外之發光之螢光染料,係可賦予使發光色發揮之更加良好的設計效果。此外亦可提供藉由極微量之染顏料進行之著色,且具有鮮豔的發色性之聚碳酸酯樹脂組成物。
(C成分:橡膠強化苯乙烯系樹脂)
本發明中適宜使用之橡膠強化苯乙烯系樹脂為將芳香族乙烯基化合物與由其他乙烯基單體及橡膠質聚合物所選出之1種以上進行共聚合所獲得之共聚物。成分中之芳香族乙烯基化合物之比例較佳為10重量%以上,更佳為30重量%以上,再更佳為40~90重量%,特佳為50~80重量%。該芳香族乙烯基化合物之比例為在C成分之全量100重量%中之比例,在混合複數之聚合物作為C成分之情況中,不需要所有的聚合物都滿足該適宜之條件。然而,較佳係在任一聚合物中,芳香族乙烯基化合物之比例皆為10重量%以上。接著針對苯乙烯系樹脂中所包含之代表性的單體化合物進行說明。
作為芳香族乙烯基化合物,可舉出苯乙烯、α-甲基苯乙烯、o-甲基苯乙烯、p-甲基苯乙烯、乙烯基二甲苯、乙基苯乙烯、二甲基苯乙烯、p-tert-丁基苯乙烯、乙烯基萘、甲氧基苯乙烯、單溴苯乙烯、二溴苯乙烯、氟苯乙烯、三溴苯乙烯等,特佳為苯乙烯。
作為可與芳香族乙烯基化合物共聚合之其他乙烯基單體,較佳可舉出氰化乙烯基化合物及(甲基)丙烯酸酯化合物。作為氰化乙烯基化合物,可舉出丙烯腈、甲基丙烯腈等,特佳為丙烯腈。
作為(甲基)丙烯酸酯化合物,具體而言可舉出甲基(甲基)丙烯酸酯、乙基(甲基)丙烯酸酯、丙基(甲基)丙烯酸酯、異丙基(甲基)丙烯酸酯、丁基(甲基)丙烯酸酯、戊基(甲基)丙烯酸酯、己基(甲基)丙烯酸酯、辛基(甲基)丙烯酸酯、2-乙基己基(甲基)丙烯酸酯、環己基(甲基)丙烯酸酯、十二烷基(甲基)丙烯酸酯、十八烷基(甲基)丙烯酸酯、苯基(甲基)丙烯酸酯、苄基(甲基)丙烯酸酯等。此外,(甲基)丙烯酸酯之記載係表示包含甲基丙烯酸酯及丙烯酸酯中之任一者,(甲基)丙烯酸酯之記載係表示包含甲基丙烯酸酯及丙烯酸酯中之任一者。作為特別適宜之(甲基)丙烯酸酯化合物,可舉出甲基甲基丙烯酸酯。
作為可與氰化乙烯基化合物及(甲基)丙烯酸酯化合物以外之芳香族乙烯基化合物共聚合之其他乙烯基單體,可舉出甲基丙烯酸縮水甘油酯等的含有環氧基之甲基丙烯酸酯、馬來醯亞胺、N-甲基馬來醯亞胺、N-苯基馬來醯亞胺等的馬來醯亞胺系單體、丙烯酸、甲基丙烯酸、馬來酸、馬來酸酐、鄰苯二甲酸、伊康酸等的α,β-不飽和羧酸及其無水物。
作為上述橡膠質聚合物,可舉出聚丁二烯、聚異戊二烯、二烯系共聚物(例如,苯乙烯・丁二烯之無規共聚物及嵌段共聚物、丙烯腈・丁二烯共聚物,以及(甲基)丙烯酸烷基酯及丁二烯之共聚物等)、乙烯與α-烯烴之共聚物(例如,乙烯・丙烯無規共聚物及嵌段共聚物、乙烯・丁烯之無規共聚物及嵌段共聚物等)、乙烯與不飽和羧酸酯之共聚物(例如乙烯・甲基丙烯酸酯共聚物,及乙烯・丁基丙烯酸酯共聚物等)、乙烯與脂肪族乙烯基之共聚物(例如,乙烯・乙酸乙烯基共聚物等)、乙烯與丙烯與非共軛二烯三元共聚物(例如,乙烯・丙烯・己二烯共聚物等)、丙烯酸系橡膠(例如,聚丁基丙烯酸酯、聚(2-乙基己基丙烯酸酯),及丁基丙烯酸酯與2-乙基己基丙烯酸酯之共聚物等),以及矽酮系橡膠(例如,聚有機矽氧烷橡膠、由聚有機矽氧烷橡膠成分與聚烷基(甲基)丙烯酸酯橡膠成分所構成之IPN型橡膠;亦即具有2個橡膠成分以無法分離的方式相互地糾結之結構之橡膠,及由聚有機矽氧烷橡膠成分與聚異丁烯橡膠成分所構成之IPN型橡膠等)。其中,更佳者為更容易表現該效果之聚丁二烯、聚異戊二烯、或二烯系共聚物,特佳為聚丁二烯。
作為橡膠強化苯乙烯系樹脂,具體而言,例如,可舉出HIPS樹脂、ABS樹脂、AES樹脂、ASA樹脂、MBS樹脂、MABS樹脂、MAS樹脂、SIS樹脂,及SBS樹脂等,皆可輕易地入手。其中,更佳者為HIPS樹脂、ABS樹脂、AES樹脂、ASA樹脂、MBS樹脂。
此等之其中,特佳為ABS樹脂、MBS樹脂。ABS樹脂對於薄型成形品具有優良之成形加工性,亦具有良好的耐衝撃性。MBS樹脂對於薄型成形品亦具有良好的耐衝撃性。尤其在與芳香族聚碳酸酯樹脂之組合中,係可表現較佳之特性。
此外,此處AES樹脂係表示主要由丙烯腈、乙烯-丙烯橡膠,及苯乙烯所成之共聚物樹脂、ASA樹脂係表示主要由丙烯腈、苯乙烯,及丙烯酸橡膠所成之共聚物樹脂、MABS樹脂係表示主要由甲基甲基丙烯酸酯、丙烯腈、丁二烯,及苯乙烯所成之共聚物樹脂、MAS樹脂係表示主要由甲基甲基丙烯酸酯、丙烯酸橡膠,及苯乙烯所成之共聚物樹脂、SIS樹脂係表示由聚苯乙烯及聚異戊二烯所構成之嵌段共聚物樹脂(若為二-嵌段以上即可,又包含經過氫化者)、SBS樹脂係表示由聚苯乙烯及聚丁二烯所構成之嵌段共聚物(若為二-嵌段以上即可,又包含經過氫化者)。
橡膠強化苯乙烯系樹脂係可單獨使用亦可併用2種以上。例如ABS樹脂與MBS樹脂之組合亦適宜在本發明中使用。
ABS樹脂中,ABS樹脂成分100重量%中(亦即ABS聚合物與AS聚合物之合計100重量%中)二烯橡膠成分之比例為5~80重量%係較佳,更佳為7~70重量%,特佳為10~60重量%。
ABS樹脂中,橡膠粒子徑之重量平均粒子徑為0.05~5μm係較佳,0.1~2.0μm係更佳,0.1~1.5μm係更佳。該橡膠粒子徑之分布為單一分布者及具有2個峰以上之複數峰者均可使用,此外,在其形態方面,可以像是橡膠粒子為單一相之型態,亦可以是通過使橡膠粒子之周圍具有包藏(occlude)相而具有薩拉米(Salami)結構之型態。
此外,ABS樹脂含有未與二烯系橡膠成分接枝之氰化乙烯基化合物及芳香族乙烯基化合物之共聚物係以往眾所皆知的。ABS樹脂係亦可含有在如同上述聚合時產生之游離的聚合物成分,此外亦可為混合將芳香族乙烯基化合物與氰化乙烯基化合物藉由其他途徑共聚合所獲得之乙烯基化合物聚合物者。
因此,橡膠強化苯乙烯系樹脂係包含將含有橡膠成分之共聚物與以其他途徑聚合所獲得之不含橡膠成分之聚合物混合後之態樣。該混合係可在製造本發明之樹脂組成物時進行,亦可在混合前先進行製造。
將氰化乙烯基化合物與芳香族乙烯基化合物進行共聚合之熱可塑性共聚物(AS共聚物)中,作為氰化乙烯基化合物,係可舉出前述者,特佳係可使用丙烯腈。此外,作為芳香族乙烯基化合物,同樣地可舉出前述者,然而較佳為苯乙烯及α-甲基苯乙烯。AS共聚物中各成分之比例,在將全體定為100重量%之情況中,氰化乙烯基化合物較佳為5~50重量%,更佳為15~35重量%,芳香族乙烯基化合物較佳為95~50重量%,更佳為85~65重量%。此外,亦可以在此等乙烯基化合物中共聚前述之可共聚合之其它乙烯系化合物,其含有比例較佳為在AS共聚物中為15重量%以下者。又,在反應中所使用之起始劑、鏈轉移劑等係可依據需要使用以往習知之各種物質。
該AS共聚物可為藉由塊狀聚合、溶液聚合、懸濁聚合、懸濁塊狀聚合,及乳化聚合等的任一方法所製造者,然而較佳為藉由塊狀聚合所製造者。又,共聚合之方法亦是藉由一階段之共聚合或多階段之共聚合之任一者均可。該AS共聚物之還原黏度為以下述記載之方法求出之還原黏度(30℃)為0.2~1.0dl/g,更佳為0.3~0.7dl/g者。
還原黏度係將AS共聚物精秤0.25g並花費2小時使其溶解於二甲基甲醯胺50ml後之溶液,使用烏氏黏度計於30℃之環境下所測定者。此外,黏度計係使用溶媒之流下時間為20~100秒者。還原黏度係由溶媒的流下秒數(t0
)及溶液的流下秒數(t)藉由以下公式求出。
還原黏度(ηsp
/C)={(t/t0
)-1}/0.5
此外,該游離的AS共聚物之比例可以透過在丙酮等的該AS共聚物之良溶媒中溶解ABS共聚物,並由其可溶成分來獲取。另一方面其不溶分(膠體)為實質的ABS共聚物。
ABS共聚物中,接枝於二烯系橡膠成分之氰化乙烯基化合物及芳香族乙烯基化合物之比例(該接枝成分之重量相對於二烯系橡膠成分之重量之比例),亦即接枝率(重量%)較佳為20~200%,更佳為20~80%。
該ABS樹脂可為藉由塊狀聚合、溶液聚合、懸濁聚合,及乳化聚合等的任一方法所製造者。更佳為藉由塊狀聚合法所製造出之ABS樹脂。此外,作為該塊狀聚合法,代表性地可例示出化學工學48卷第6號415頁(1984)所記載之連續塊狀聚合法(亦即東麗法),以及化學工學第53卷第6號423頁(1989)所記載之連續塊狀聚合法(亦即三井東壓法)。作為ABS樹脂,係任一ABS樹脂皆適宜使用。又,共聚合之方法亦可適用一階段共聚合,亦可使用多階段共聚合。
在MBS樹脂中,MBS樹脂成分100重量%中,二烯橡膠成分之比例較佳為30~90重量%,更佳為40~85重量%,特佳為50~80重量%。
在MBS樹脂中,橡膠粒子徑之重量平均粒子徑較佳為0.05~2μm,更佳為0.1~1.0μm,再更佳為0.1~0.5μm。該橡膠粒子徑之分布為單一分布者及具有2個峰以上之複數峰者均可使用。該MBS樹脂較佳係可使用以乳化聚合製造者。
相對於(A)聚碳酸酯樹脂(A成分)100重量份,較佳係含有(C)橡膠強化苯乙烯系樹脂(C成分)1~100重量份,更佳係含有5~80重量份,再更佳係含有10~50重量份,特佳係含有15~40重量份。橡膠強化苯乙烯系樹脂之含量若介於上述範圍,則具有良好的耐衝撃性及優良之成形加工性。
(D成分:合成雲母粉以外之無機充填材)
可適宜使用本發明中之合成雲母粉以外之無機充填材。作為無機充填材,可例示出滑石、矽灰石、碳酸鈣、玻璃纖維、玻璃珠、玻璃中空球、玻璃磨碎纖維、玻璃薄片、碳纖維、碳薄片、碳珠、碳磨碎纖維、石墨、奈米碳管、金屬薄片、金屬纖維、塗覆金屬之玻璃纖維、塗覆金屬之碳纖維、塗覆金屬之玻璃薄片、二氧化矽、金屬氧化物粒子、金屬氧化物纖維、金屬氧化物中空球,以及各種晶鬚(鈦酸鉀晶鬚、硼酸鋁晶鬚,及鹼性硫酸鎂等)等。其中,由機械的強度及成形品之外觀的觀點來看,較佳係使用由滑石及矽灰石所成之群所選出之至少1種無機充填劑。
所謂滑石,以化學組成而言為含水矽酸鎂,一般而言係以化學式4SiO2
・3MgO・2H2
O表示,為具有一般層狀結構之鱗片狀之粒子,此外,以組成而言,係由SiO2
56~65重量%、MgO 28~35重量%、H2
O約5重量%左右所構成。作為其他的少量成分,係含有Fe2
O3
0.03~1.2重量%、Al2
O3
0.05~1.5重量%、CaO 0.05~1.2重量%、K2
O 0.2重量%以下,Na2
O 0.2重量%以下等。滑石之粒子徑,較佳係藉由沈降法所測定之平均粒徑為0.1~15μm(更佳為0.2~12μm,再更佳為0.3~10μm,特佳為0.5~5μm)之範圍。並且特佳係使用使體積密度為0.5(g/cm3
)以上之滑石作為原料。滑石之平均粒徑是指採用作為液相沈降法之一的X線透過法測得之D50(粒子徑分布之中值徑)。作為進行該測定之裝置之具體例,可舉出Micromeritics公司製Sedigraph5100等。
另外,對於從原石粉碎滑石時之製法係沒有特別限制,可利用軸流型研磨法、環型研磨法、輥磨法、球磨法、噴射磨法,及容器旋轉式壓縮剪切型研磨法等。此外,粉碎後之滑石利用各種分級機進行分級處理,較佳係粒子徑之分布整齊者。作為分級機,係沒有特別限制,可舉出衝擊型慣性力分級機(可變式衝擊器等)、康達效果(coanda effect)利用型慣性力分級機(彎頭噴射器(elbow jet)等)、遠心場分級機(多段旋風器、微粉分粒機(microplex)、分散分粒機(dispersion separator)、艾丘卡特分級機(Accu-Cut)、渦輪分級機、渦輪分粒機、離心式分粒機(micronseparator),及超級分粒機(super separator)等)等。此外,滑石粉係就其操作性等而言,以凝集狀態者為佳,作為其之製法,係有藉由脫氣壓縮之方法、使用集束劑而進行壓縮之方法等。特別是藉由脫氣壓縮之方法係簡便且不需要之集束劑樹脂成分不會混入至本發明的樹脂組成物中,因而較佳。
矽灰石之纖維直徑較佳為0.1~10μm,更佳為0.1~5μm,再更佳為0.1~3μm。此外其長徑比(平均纖維長度/平均纖維直徑)較佳為3以上。作為長徑比之上限,可舉出30以下。此處纖維直徑係使用電子顯微鏡觀察強化填料,且求取各個之纖維直徑,並且從其測定值算出數量平均纖維直徑。使用電子顯微鏡係因為使用光學顯微鏡正確地測定作為對象的水準之大小係困難的。纖維直徑係對在電子顯微鏡的觀察所得到之影像,無規地抽出測定纖維直徑之對象的填料且在接近中央部位置測定纖維直徑,而且從所得到的測定值算出數量平均纖維直徑。觀察倍率係設為約1000倍,測定根數係500根以上(作業上係使用600根以下為宜)來進行。另一方面,平均纖維長度的測定係使用光學顯微鏡觀察填料且求取各根的長度,並且從其測定值算出數量平均纖維長度。光學顯微鏡的觀察係從準備填料之間以不過度互相重疊的方式分散而成之試樣開始。觀察係在物鏡20倍的條件下進行且將其觀察影像收容在像素數為約25萬之CCD相機作為影像數據。將所得到的影像數據使用影像解析裝置且使用求取影像數據之2點間的最大距離之程式,而算出纖維長度。在此種條件下,每1像素的大小係相當於1.25μm之長度且係以測定根數為500根以上(作業上係使用600根以下為宜)來進行。
矽灰石係因為樹脂組成物充分反應其原本所具有的白色度,故宜以磁選機強力去除混入原料礦石中的鐵成分,以及在將原料礦石粉碎時因機器的磨損而混入的鐵成分。藉由該磁選機處理,矽灰石中之鐵之含量在換算為Fe2
O3
之情況下,較佳為0.5重量%以下。
矽酸鹽礦物(更佳為雲母、滑石、矽灰石)係以未表面處理為佳,但亦可使用矽烷耦合劑、高級脂肪酸酯,及蠟等的各種表面處理劑進行表面處理。而且亦可以使用各種樹脂、高級脂肪酸酯,及蠟等的集束劑進行造粒而成為顆粒狀。
相對於(A)聚碳酸酯樹脂(A成分)100重量份,較佳係含有(D)合成雲母粉以外之無機充填材(D成分)1~100重量份,更佳係含有5~80重量份,再更佳係含有10~60重量份,特佳係含有20~50重量份。合成雲母粉以外之無機充填劑之含量若介於上述範圍,則具有良好的機械特性及成形品外觀。
(E成分:阻燃劑)
本發明中係可適宜地使用阻燃劑。作為阻燃劑,可使用屬於已知對於芳香族聚碳酸酯發揮阻燃性之磷酸酯、磺酸鹼(土類)金屬鹽、矽酮系化合物等。
作為阻燃劑使用之磷酸酯係可使用各種習知可對於芳香族聚碳酸酯發揮阻燃性之磷酸酯。其中,更佳為以下述一般式(III)表示者。此外,下述一般式(III)中之芳基,係指將芳香族化合物之苯環去除1個氫原子後之殘基。較佳為將芳香族烴之苯環去除1個氫原子後殘基。作為芳基,例如可舉出苯基、甲苯基、二甲苯基、聯苯基,及萘基等。
(此處R1、R2、R3及R4係各自獨立為碳數6~12之芳基,R5及R6係各自獨立地表示甲基或氫原子,R7及R8係表示甲基,m1及m2係各自獨立地表示0~2之整數,a、b、c及d係各自獨立為0或1,且n為1至5之整數。)
作為磷酸酯,較佳係在一般式(III)中,m1及m2為0,a、b、c,及d為1,R1、R2、R3,及R4為苯基,以及R5及R6為甲基之態樣。由於以該雙酚A雙(二苯基磷酸酯)為主成分之磷酸酯之磷含量高,故包含其之樹脂組成物之阻燃性良好,成形時之流動性亦良好。此外由於該磷酸酯之結構上耐水解性亦為良好,故包含其之樹脂組成物之長期的品質保持性亦優良。
更適宜作為阻燃劑之磷酸酯為上述一般式(III),其中其酸價為0.2mgKOH/g以下,且為下述一般式(IV)所示之磷酸酯化合物(以下亦稱為“半酯”)之含量為1.5重量%以下者。
(此處R1及R2係各自獨立為碳數6~12之芳基,R5及R6係各自獨立地表示甲基或氫原子,R7及R8係表示甲基,m1及m2係各自獨立地表示0~2之整數,a及b係各自獨立為0或1。)
磷酸酯之酸價更佳為0.15mgKOH/g以下,再更佳為0.1mgKOH/g以下,特佳為0.05mgKOH/g以下。該酸價之下限係實質上可定為0,實際應用上較佳為0.01mgKOH/g以上。另一方面,半酯之含量更佳為1.1重量%以下,再更佳為0.9重量%以下。作為下限,實際應用上較佳為0.1重量%以上係較佳,更佳為0.2重量%以上。在酸價超過0.2mgKOH/g之情況中,或在半酯含量超過1.5重量%之情況中,成形時之熱穩定性變差,且伴隨著芳香族聚碳酸酯之分解,樹脂組成物之耐水解性係降低。
磷酸酯較佳係包含100重量%中縮合度n之各自的比例為n=0之成分0.1~3重量%,更佳為0.5~2.5重量%,n=1之成分85~98.5重量%,更佳為89.5~98.5重量%,n=2之成分1~9重量%,更佳為1~7重量%,及n≧3之成分1.5重量%以下,更佳為1重量%以下之比例,且將n=0之成分排除而算出之重量平均縮合度N為1.01~1.10,較佳為1.01~1.09,更佳為1.01~1.07。具有該分布之B成分,係優異地兼具樹脂組成物之耐熱性及耐衝撃性。此外,上述所謂各n成分,係指由特定的二價酚及一價酚所合成之成分,係不包含反應副產物等。例如使用苯酚作為一價酚之情況中,n=0之成分為三苯基磷酸酯。
作為阻燃劑使用之所謂磺酸鹼(土類)金屬鹽,係指全氟烷基磺酸與鹼金屬或鹼土類金屬之金屬鹽,或芳香族磺酸與鹼金屬或鹼土類金屬鹽之金屬鹽。
作為構成金屬鹽之鹼金屬,可舉出鋰、鈉、鉀、銣及銫,作為鹼土類金屬,可舉出鈹、鎂、鈣、鍶及鋇。更佳為鹼金屬。該鹼金屬之中,在對於透明性有更高要求之情況中,較佳為銣及銫,另一方面,由於此等並非通用且亦難以精製,故就結果而言因成本而有不利之情況。另一方面,雖在成本及阻燃性上為有利,然而鋰及鈉係反而在透明性上有不利之情況。考慮此等後,可分開使用磺酸鹼金屬鹽中之鹼金屬,但是在上述任一方面,最佳為特性平衡優良之磺酸鉀鹽。可併用包含該鉀鹽與其他鹼金屬之磺酸鹼金屬鹽。
作為全氟烷基磺酸鹼金屬鹽之具體例,可舉出三氟甲烷磺酸鉀、全氟丁烷磺酸鉀、全氟己烷磺酸鉀、全氟辛烷磺酸鉀、五氟乙烷磺酸鈉、全氟丁烷磺酸鈉、全氟辛烷磺酸鈉、三氟甲烷磺酸鋰、全氟丁烷磺酸鋰、全氟庚烷磺酸鋰、三氟甲烷磺酸銫、全氟丁烷磺酸銫、全氟辛烷磺酸銫、全氟己烷磺酸銫、全氟丁烷磺酸銣,及全氟己烷磺酸銣等,此等係可使用1種或者併用2種以上來使用。此處全氟烷基之碳數較佳為1~18之範圍,更佳為1~10之範圍,再更佳為1~8之範圍。此等之中特佳為全氟丁烷磺酸鉀。
作為芳香族磺酸鹼(土類)金屬鹽之具體例,例如可舉出二苯基硫醚-4,4’-二磺酸二鈉、二苯基硫醚-4,4’-二磺酸二鉀、5-磺酸基異酞酸鉀、5-磺酸基異酞酸鈉、聚伸乙基對酞酸聚磺酸鈉、1-甲氧基萘-4-磺酸鈣、4-十二烷基苯基醚二磺酸二鈉、聚(2,6-二甲基伸苯基氧化物)聚磺酸聚鈉、聚(1,3-伸苯基氧化物)聚磺酸聚鈉、聚(1,4-伸苯基氧化物)聚磺酸聚鈉、聚(2,6-二苯基伸苯基氧化物)聚磺酸聚鉀、聚(2-氟-6-丁基伸苯基氧化物)聚磺酸鋰、苯磺酸鹽之磺酸鉀、苯磺酸鈉、苯磺酸鍶、苯磺酸鎂、p-苯二磺酸二鉀、萘-2,6-二磺酸二鉀、聯苯基-3,3’-二磺酸鈣、二苯基碸-3-磺酸鈉、二苯基碸-3-磺酸鉀、二苯基碸-3,3’-二磺酸二鉀、二苯基碸-3,4’-二磺酸二鉀、α,α,α-三氟苯乙酮-4-磺酸鈉、二苯甲酮-3,3’-二磺酸二鉀、噻吩-2,5-二磺酸二鈉、噻吩-2,5-二磺酸二鉀、噻吩-2,5-二磺酸鈣、苯并噻吩磺酸鈉、二苯基亞碸-4-磺酸鉀、萘磺酸鈉之甲醛縮合物,及蒽磺酸鈉之甲醛縮合物等。此等芳香族磺酸鹼(土類)金屬鹽中,特佳為鉀鹽。
作為阻燃劑使用之矽酮系化合物為具有矽氧烷鍵結之化合物,且為藉由燃燒時之化學反應使阻燃性提高者,可使用習知作為芳香族聚碳酸酯樹脂之阻燃劑而被提案出之各種化合物。矽酮化合物被認為係藉由燃燒時自體鍵結或與源自樹脂之成分鍵結形成之架構,或藉由該架構形成時之還原反應,來賦予聚碳酸酯樹脂難燃效果者。因此該反應中,較佳係包含活性高之基,更具體而言較佳係包含特定量之由烷氧基及氫(亦即Si-H基)所選出之至少1種基。作為該基(烷氧基、Si-H基)之含有比例,較佳為在0.1~1.2mol/100g之範圍內,更佳為在0.12~1mol/100g之範圍內,再更佳為在0.15~0.6mol/100g之範圍內。該比例係可藉由鹼分解法,並藉由測定矽酮化合物之每單元重量所產生之氫或醇之量來求出。此外,烷氧基較佳為碳數1~4之烷氧基,特佳為甲氧基。
一般而言,矽酮化合物之結構係藉由將以下所示之4種類之矽氧烷單元任意地組合而構成。亦即,
M單元:(CH3
)3
SiO1/2
、H(CH3
)2
SiO1/2
、H2
(CH3
)SiO1/2
、(CH3
)2
(CH2
=CH)SiO1/2
、(CH3
)2
(C6
H5
)SiO1/2
、
(CH3
)(C6
H5
)(CH2
=CH)SiO1/2
等的1官能性矽氧烷單元、
D單元:(CH3
)2
SiO、H(CH3
)SiO、H2
SiO、H(C6
H5
)SiO、(CH3
)(CH2
=CH)SiO、(C6
H5
)2
SiO等的2官能性矽氧烷單元、
T單元:(CH3
)SiO3/2
、(C3
H7
)SiO3/2
、HSiO3/2
、(CH2
=CH)SiO3/2
、(C6
H5
)SiO3/2
等的3官能性矽氧烷單元、
O單元:為以SiO2
表示之4官能性矽氧烷單元。
矽酮系化合物之結構,具體而言,作為示性式可舉出Dn
、Tp
、Mm
Dn
、Mm
Tp
、Mm
Qq
、Mm
Dn
Tp
、Mm
Dn
Qq
、Mm
Tp
Qq
、Mm
Dn
Tp
Qq
、Dn
Tp
、Dn
Qq
、Dn
Tp
Qq
。其中較佳之矽酮化合物之結構為Mm
Dn
、Mm
Tp
、Mm
Dn
Tp
、Mm
Dn
Qq
,再更佳之結構為Mm
Dn
或Mm
Dn
Tp
。
此處,前述示性式中之係數m、n、p、q係表示各矽氧烷單元之聚合度之1以上之整數,各示性式中,係數之合計為矽酮化合物之平均聚合度。此平均聚合度較佳為3~150之範圍,更佳為3~80之範圍,再更佳為3~60之範圍,特佳為4~40之範圍。該在越適宜的範圍內,良好的阻燃性係變得越優良。此外,如同後述,包含特定量之芳香族基之矽酮化合物之透明性亦優良。又,m、n、p、q中之任一者為2以上之數值之情況中,附有該係數之矽氧烷單元中,可以是鍵結之氫原子或有機殘基為不同之2種以上之矽氧烷單元。
此外,矽酮系化合物可為直鏈狀亦可為具有分支結構者。又,鍵結於矽酮原子之有機殘基之碳數較佳為1~30,更佳為1~20之有機殘基。作為該有機殘基,具體而言,可舉出甲基、乙基、丙基、丁基、己基、癸基等的烷基、環己基等的環烷基、苯基、甲苯基等的芳基及芳烷基。再更佳為碳數1~8之烷基、烯基或芳基。作為烷基,特佳為甲基、乙基、丙基等的碳數1~4之烷基。
此外,矽酮系化合物含有芳基之情況,係由於可提供阻燃性及透明性更優良之芳香族聚碳酸酯樹脂組成物,故而較佳。更佳而言,下述一般式(V)所示之芳香族基所包含之比例(芳香族基量)較佳為10~70重量%(更佳為15~60重量%)。
(式(V)中,X係各自獨立地表示OH基、碳數1~20之一價有機殘基。n係表示0~5之整數。此外,式(V)中之n為2以上之情況中,係可選擇互相相異之種類之X。)
矽酮系化合物中除了前述Si-H基及烷氧基以外,亦可含有反應基,作為該反應基,例如,可例示出胺基、羧基、環氧基、乙烯基、巰基,及甲基丙烯醯氧基等。
相對於(A)聚碳酸酯樹脂(A成分)100重量份,較佳係含有(E)阻燃劑(E成分)1~100重量份,更佳係含有5~70重量份,再更佳係含有10~50重量份,特佳係含有20~40重量份。阻燃劑之含量若介於上述範圍,則具有良好的阻燃性及機械的物性。
(F成分:防滴落劑)
本發明之聚碳酸酯樹脂組成物係可含有防滴落劑作為F成分。藉由含有該防滴落劑,係可不損害成形品之物性且達成良好的阻燃性。
作為防滴落劑,可舉出具有原纖維形成能之含氟聚合物,作為該聚合物,可舉出聚四氟乙烯、四氟乙烯系共聚物(例如,四氟乙烯/六氟丙烯共聚物、等)、如同美國專利第4379910號公報所示之部分氟化聚合物、由氟化聯苯酚所製造之聚碳酸酯樹脂等。其中,較佳為聚四氟乙烯(以下亦稱為PTFE)。
具有原纖維形成能力之PTFE的分子量係具有非常高的分子量,藉由剪切力等的外部作用,PTFE之間進行鍵結而顯示成為纖維狀之傾向者。其分子量係在從標準比重所求取的數量平均分子量,為100萬~1000萬,更佳為200萬~900萬。該PTFE係除了固體形狀以外,亦能夠使用水性分散液形態者。又,該具有原纖維形成能之PTFE係為了使樹脂中的分散性提升且得到更良好的阻燃性及機械特性,亦可以使用與其他樹脂之混合形態之PTFE混合物。
作為該具有原纖維形成能之PTFE之市售品,可舉出例如Dupont Mitsui Fluorochemicals(股)之鐵氟龍(註冊商標)6J、大金工業(股)之Polyflon MPA FA500及F-201L等。作為PTFE之水性分散液之市售品,可舉出Asahi ICI Fluoropolymers(股)製之Fluon AD-1、AD-936、大金工業(股)製之Fluon D-1及D-2、Dupont Mitsui Fluorochemicals (股)製之鐵氟龍(註冊商標)30J等作為代表。
作為混合形態之PTFE,係可使用藉由以下方式獲得者:(1)將PTFE之水性分散液與有機聚合物之水性分散液或溶液進行混合並進行共沉澱,獲得共凝集混合物之方法(日本特開昭60-258263號公報、日本特開昭63-154744號公報等所記載之方法)、(2)將PTFE之水性分散液與乾燥後之有機聚合物粒子混合之方法(日本特開平4-272957號公報所記載之方法)、(3)將PTFE之水性分散液與有機聚合物粒子溶液均勻地混合,由該混合物將各自之介質同時地除去之方法(日本特開平06-220210號公報、日本特開平08-188653號公報等所記載之方法)、(4)於PTFE之水性分散液中將形成有機聚合物之單體聚合之方法(日本特開平9-95583號公報所記載之方法),及(5)將PTFE之水性分散液與有機聚合物分散液均勻地混合後,進一步於該混合分散液中聚合乙烯系單體,並於其後獲得混合物之方法(日本特開平11-29679號等所記載之方法)。作為此等混合形態之PTFE之市售品,可舉出三菱麗陽(股)之「Metablen A3800」(商品名),及GESPECIALTY CHEMICALS CO., Ltd.公司製「BLENDEX B449」(商品名)等。
作為混合形態中之PTFE之比例,在 PTFE混合物100重量%中,PTFE較佳為1~60重量%,更佳為5~55重量%。PTFE之比例介於該範圍內之情況中,PTFE可達成良好的分散性。此外,上述F成分之比例係表示實質上防滴落劑之量,在混合形態之PTFE之情況中,係表示實質上之PTFE量。
相對於(A)聚碳酸酯樹脂(A成分)100重量份,較佳係含有(F)防滴落劑(F成分)0.01~10重量份,更佳係含有0.1~5重量份,再更佳係含有0.3~3重量份,特佳係含有0.5~2重量份。防滴落劑之含量若介於上述範圍,則有優良之阻燃性及良好的成形品表面外觀。
此外,作為聚四氟乙烯系混合體中所使用之有機系聚合物中所使用之苯乙烯系單體,可例示出可被碳數1~6之烷基、碳數1~6之烷氧基及鹵素所成之群所選出之1個以上之基取代之苯乙烯,例如,鄰-甲基苯乙烯、間-甲基苯乙烯、對-甲基苯乙烯、二甲基苯乙烯、乙基-苯乙烯、對-tert-丁基苯乙烯、甲氧基苯乙烯、氟苯乙烯、單溴苯乙烯、二溴苯乙烯,及三溴苯乙烯、乙烯基二甲苯、乙烯基萘,然而並不限定於此等。前述苯乙烯系單體係可單獨或將2個以上之種類混合使用。
聚四氟乙烯系混合體中所使用之有機系聚合物中所使用之丙烯酸系單體係包含可被取代之(甲基)丙烯酸酯衍生物。具體而言,作為前述丙烯酸系單體,可例示出可被由碳數1~20之烷基、碳數3~8之環烷基、芳基,及環氧丙基所成之群所選出之1個以上之基取代之(甲基)丙烯酸酯衍生物,例如(甲基)丙烯腈、甲基(甲基)丙烯酸酯、乙基(甲基)丙烯酸酯、丙基(甲基)丙烯酸酯、丁基(甲基)丙烯酸酯、戊基(甲基)丙烯酸酯、己基(甲基)丙烯酸酯、2-乙基己基(甲基)丙烯酸酯、環己基(甲基)丙烯酸酯、辛基(甲基)丙烯酸酯、十二烷基(甲基)丙烯酸酯、苯基(甲基)丙烯酸酯、苄基(甲基)丙烯酸酯及環氧丙基(甲基)丙烯酸酯、可被碳數1~6之烷基、或芳基取代之馬來醯亞胺,例如,馬來醯亞胺、N-甲基-馬來醯亞胺及N-苯基-馬來醯亞胺、馬來酸、鄰苯二甲酸及伊康酸,然而並不限於此等。前述丙烯酸系單體係可單獨或將2個以上之種類混合使用。此等之其中,較佳為(甲基)丙烯腈。
用於塗佈層之有機聚合物所包含之源自丙烯酸系單體之單元之量,相對於源自苯乙烯系單體之單元100重量份,較佳為8~11重量份,更佳為8~10重量份,再更佳為8~9重量份。源自丙烯酸系單體之單元若少於8重量份,則有塗佈強度降低之情況,若大於11重量份則成形品之表面外觀有變差的可能。
聚四氟乙烯系混合體之殘存水分含量較佳為0.5重量%以下,更佳為0.2~0.4重量%,再更佳為0.1~0.3重量%。殘存水分量若大於0.5重量%,則有可能對於阻燃性帶來不良之影響。
聚四氟乙烯系混合體之製造步驟中,係包含在起始劑的存在下,於分支狀聚四氟乙烯之外部形成塗佈層之步驟,且該塗佈層係包含由苯乙烯系單體及丙烯酸單體所成之群組所選出之1個以上之單體。進而,較佳係包含在前述塗佈層形成之步驟後,以使殘存水分含量成為0.5重量%以下,較佳為0.2~0.4重量%,更佳為0.1~0.3重量%的方式進行乾燥之步驟。乾燥之步驟係可使用例如,如同熱風乾燥或真空乾燥方法那樣本發明技術領域習知之方法來進行。
聚四氟乙烯系混合體中所使用之起始劑,若為苯乙烯系及/或丙烯酸系單體之聚合反應中所使用者則可無限制地使用。作為前述起始劑,可例示出異丙苯基過氧化氫、二-tert-丁基過氧化物、苯甲醯基過氧化物、過氧化氫,及過氧化鉀,然而並不限於此等。本發明之聚四氟乙烯系混合體中,依據反應條件可使用1種以上之前述起始劑。前述起始劑之量係可在考慮聚四氟乙烯之量及單體之種類/量後,在可使用之範圍內自由地選擇,較佳係以全組成物之量作為基準,使用0.15~0.25重量份。
此外,可使用被覆分支PTFE作為防滴落劑。被覆分支PTFE為包含分支狀聚四氟乙烯粒子及有機系聚合物之聚四氟乙烯系混合體,分支狀聚四氟乙烯之外部係具有包含有機系聚合物之塗佈層,較佳為具有包含源自苯乙烯系單體之單元及/或源自丙烯酸系單體之單元之聚合物之塗佈層。前述塗佈層係形成於分支狀聚四氟乙烯之表面上。此外,前述塗佈層較佳係包含苯乙烯系單體及丙烯酸系單體之共聚物。
被覆分支PTFE所包含之聚四氟乙烯為分支狀聚四氟乙烯。在所包含之聚四氟乙烯非分支狀聚四氟乙烯之情況下,聚四氟乙烯之添加為較少之情況,其防止滴落之效果係不充分。分支狀聚四氟乙烯為粒子狀,較佳係0.1~0.6μm,更佳係0.3~0.5μm,再更佳係具有0.3~0.4μm之粒子徑。粒子徑小於0.1μm之情況中,雖然成形品的表面外觀優良,然而在商業上取得具有粒子徑小於0.1μm之聚四氟乙烯係困難的。又,粒子徑大於0.6μm時,成形品的表面外觀有變差之情況。本發明中所使用之聚四氟乙烯之數量平均分子量較佳為1×104
~1×107
,更佳為2×106
~9×106
,一般而言,高分子量的聚四氟乙烯係在穩定性方面較佳。粉末或分散液的形態均可使用。被覆分支PTFE中,分支狀聚四氟乙烯之含量相對於被覆分支PTFE之總重量100重量份,較佳為20~60重量份,更佳為40~55重量份,再更佳為47~53重量份,特佳為48~52重量份,最佳為49~51重量份。分支狀聚四氟乙烯之比例介於該範圍內之情況中,分支狀聚四氟乙烯可達成良好的分散性。
(G成分:脫模劑)
本發明係可適宜地使用脫模劑。本發明之聚碳酸酯樹脂組成物中,以提升其成形時之生產性及降低成形品之變形為目的,較佳係更進一步摻合脫模劑。作為該脫模劑,可使用習知者。例如,可舉出飽和脂肪酸酯、不飽和脂肪酸酯、聚烯烴系蠟(聚乙烯蠟、1-烯烴聚合物等。可使用以含有酸改質等的官能基之化合物進行改質者)、矽酮化合物、氟化合物(以聚氟烷基醚為代表之氟油等)、石蠟、蜜蠟等。
其中,作為較佳之脫模劑可舉出脂肪酸酯。該脂肪酸酯為脂肪族醇與脂肪族羧酸之酯。該脂肪族醇可為1元醇亦可為2元以上之多元醇。又作為該醇之碳數,係3~32之範圍,更佳為5~30之範圍。作為該一元醇,例如可例示出十二醇、十四醇、十六醇、十八醇、二十醇、二十四醇、蠟醇,及三十醇等。作為該多元醇,可舉出季戊四醇、二季戊四醇、三季戊四醇、聚甘油(三甘油~六甘油)、雙三羥甲基丙烷、木糖醇(xylitol)、山梨糖醇,及甘露糖醇等。本發明之脂肪酸酯更佳為多元醇。
另一方面,脂肪族羧酸較佳為碳數3~32,特佳為碳數10~22之脂肪族羧酸。作為該脂肪族羧酸,例如可舉出癸烷酸、十一烷酸、十二烷酸、十三烷酸、十四烷酸、十五烷酸、十六烷酸(棕櫚酸)、十七烷酸、十八烷酸(硬脂酸)、十九烷酸、二十二酸、二十烷酸,及二十二烷酸等的飽和脂肪族羧酸,以及棕櫚油酸、油酸、亞麻油酸、次亞麻油酸、二十烯酸、二十碳五烯酸,及鯨油酸等的不飽和脂肪族羧酸。上述之中,脂肪族羧酸較佳為碳原子數14~20者。其中,較佳為飽和脂肪族羧酸。特佳為硬脂酸及棕櫚酸。
硬脂酸及棕櫚酸等上述脂肪族羧酸通常由以牛油及豬油等為代表之動物性油脂及以棕櫚油或紅花子油為代表之植物性油脂等的天然油脂類製造,故此等之脂肪族羧酸通常是含有碳原子數不同的其他的羧酸成分之混合物。因此本發明之脂肪酸酯之製造中較佳亦係使用由該天然油脂類所製造之,由包含其他羧酸成分之混合物之形態構成之脂肪族羧酸,尤其較佳係使用硬脂酸或棕櫚酸。
脂肪酸酯可為部分酯及全酯(full ester)中之任一者。然而由在部分酯中,通常羥基價變高而容易誘發高溫時之樹脂之分解等之觀點來看,更佳為全酯。脂肪酸酯中,由熱穩定性之觀點來看,酸價較佳係在20以下,更佳為在4~20之範圍內,再更佳為在4~12之範圍內。此外,酸價實質上可為0。又,脂肪酸酯之羥基價更佳係在0.1~30之範圍。此外,碘價較佳為10以下。此外,碘價實質上可為0。此等之特性係可藉由JIS K 0070中所規定之方法來求取。
相對於(A)聚碳酸酯樹脂(A成分)100重量份,較佳係含有(G)脫模劑(G成分)0.01~10重量份,更佳係含有0.05~5重量份,再更佳係含有0.1~4重量份,特佳係含有0.5~3重量份。脫模劑之含量若介於上述範圍,則在成形時具有優良之離型性,且成形品之表面外觀係變得良好。
(其他添加劑)
(i)磷系穩定劑
本發明之樹脂組成物係可含有磷系穩定劑。作為磷系穩定劑,係可例示出亞磷酸、磷酸、亞膦酸、膦酸及此等之酯,以及第3級膦等。
具體而言作為亞磷酸酯化合物,係可舉出例如,三苯基亞磷酸酯、三(壬基苯基)亞磷酸酯、十三烷基亞磷酸酯、三辛基亞磷酸酯、三十八烷基亞磷酸酯、二癸基單苯基亞磷酸酯、二辛基單苯基亞磷酸酯、二異丙基單苯基亞磷酸酯、單丁基二苯基亞磷酸酯、單癸基二苯基亞磷酸酯、二辛基二苯基亞磷酸酯、三(二乙基苯基)亞磷酸酯、三(二-iso-丙基苯基)亞磷酸酯、三(二-n-丁基苯基)亞磷酸酯、三(2,4-二-tert-丁基苯基)亞磷酸酯、三(2,6-二-tert-丁基苯基)亞磷酸酯、二硬脂醯基季戊四醇二亞磷酸酯、雙(2,4-二-tert-丁基苯基)季戊四醇二亞磷酸酯、雙(2,6-二-tert-丁基-4-甲基苯基)季戊四醇二亞磷酸酯、雙(2,6-二-tert-丁基-4-乙基苯基)季戊四醇二亞磷酸酯、雙{2,4-雙(1-甲基-1-苯基乙基)苯基}季戊四醇二亞磷酸酯、苯基雙酚A季戊四醇二亞磷酸酯、雙(壬基苯基)季戊四醇二亞磷酸酯,及二環己基季戊四醇二亞磷酸酯等。
進而作為其他亞磷酸酯化合物,亦可使用與二價酚類反應且具有環狀結構者。例如,可例示出2,2’-亞甲基雙(4,6-二-tert-丁基苯基)(2,4-二-tert-丁基苯基)亞磷酸酯、2,2’-亞甲基雙(4,6-二-tert-丁基苯基)(2-tert-丁基-4-甲基苯基)亞磷酸酯,及2,2-亞甲基雙(4,6-二-tert-丁基苯基)辛基亞磷酸酯等。
作為磷酸酯化合物,可舉出磷酸三丁酯、磷酸三甲酯、磷酸三甲苯酯、磷酸三苯酯、磷酸三氯苯酯、磷酸三乙酯、磷酸二苯基甲苯基酯、磷酸二苯基單鄰聯苯基酯、磷酸三丁氧基乙酯、磷酸二丁酯、磷酸二辛酯、磷酸二異丙酯等,較佳為三苯基磷酸酯、三甲基磷酸酯。
作為亞膦酸酯化合物,可舉出四(2,4-二-tert-丁基苯基)-4,4’-伸聯苯基二亞膦酸酯、四(2,4-二-tert-丁基苯基)-4,3’-伸聯苯基二亞膦酸酯、四(2,4-二-tert-丁基苯基)-3,3’-伸聯苯基二亞膦酸酯、四(2,6-二-tert-丁基苯基)-4,4’-伸聯苯基二亞膦酸酯、四(2,6-二-tert-丁基苯基)-4,3’-伸聯苯基二亞膦酸酯、四(2,6-二-tert-丁基苯基)-3,3’-伸聯苯基二亞膦酸酯、雙(2,4-二-tert-丁基苯基)-4-苯基-苯基亞膦酸酯、雙(2,4-二-tert-丁基苯基)-3-苯基-苯基亞膦酸酯、雙(2,6-二-n-丁基苯基)-3-苯基-苯基亞膦酸酯、雙(2,6-二-tert-丁基苯基)-4-苯基-苯基亞膦酸酯、雙(2,6-二-tert-丁基苯基)-3-苯基-苯基亞膦酸酯等,更佳為四(二-tert-丁基苯基)-伸聯苯基二亞膦酸酯、雙(二-tert-丁基苯基)-苯基-苯基亞膦酸酯係較佳,四(2,4-二-tert-丁基苯基)-伸聯苯基二亞膦酸酯、雙(2,4-二-tert-丁基苯基)-苯基-苯基亞膦酸酯。該亞膦酸酯化合物係可以與上述具有取代有2個以上烷基之芳基之亞磷酸酯化合物併用故較佳。
作為膦酸酯化合物,可舉出苯膦酸二甲酯、苯膦酸二乙酯,及苯膦酸二丙酯等。
作為第3級膦,係例示出三乙基膦、三丙基膦、三丁基膦、三辛基膦、三戊基膦、二甲基苯基膦、二丁基苯基膦、二苯基甲基膦、二苯基辛基膦、三苯基膦、三-p-甲苯基膦、三萘基膦,及二苯基苄基膦等。特佳之第3級膦為三苯基膦。
作為亞膦酸酯化合物,四(2,4-二-tert-丁基苯基)-伸聯苯基二亞膦酸酯係較佳,以該亞膦酸酯為主成分之穩定劑,係作為Sandostab P-EPQ(商標、Clariant公司製)及Irgafos P-EPQ(商標、CIBA SPECIALTY CHEMICALS公司製)於市面上販售,且可使用任一者。
此外,更加適宜之亞磷酸酯化合物為二硬脂醯基季戊四醇二亞磷酸酯、雙(2,4-二-tert-丁基苯基)季戊四醇二亞磷酸酯、雙(2,6-二-tert-丁基-4-甲基苯基)季戊四醇二亞磷酸酯,及雙{2,4-雙(1-甲基-1-苯基乙基)苯基}季戊四醇二亞磷酸酯。
二硬脂醯基季戊四醇二亞磷酸酯係作為Adecastab PEP-8(商標、旭電化工業(股)製)、JPP681S(商標、城北化學工業(股)製)於市面上販售,且可使用任一者。雙(2,4-二-tert-丁基苯基)季戊四醇二亞磷酸酯係作為Adecastab PEP-24G(商標、旭電化工業(股)製)、Alkanox P-24(商標、Great Lakes公司製)、Ultranox P626(商標、GE Specialty Chemicals公司製)、Doverphos S-9432(商標、Dover Chemical公司製),以及Irgaofos126及126FF(商標、CIBA SPECIALTY CHEMICALS公司製)等於市面上販售,且可使用任一者。雙(2,6-二-tert-丁基-4-甲基苯基)季戊四醇二亞磷酸酯係作為Adecastab PEP-36(商標、旭電化工業(股)製)於市面上販售且可容易地利用。此外雙{2,4-雙(1-甲基-1-苯基乙基)苯基}季戊四醇二亞磷酸酯係作為Adecastab PEP-45(商標、旭電化工業(股)製),及Doverphos S-9228(商標、Dover Chemical公司製)於市面上販售,且可使用任一者。
上述磷系穩定劑係可單獨或將2種以上組合使用。磷系穩定劑之含量係相對於聚碳酸酯樹脂100重量份,較佳為0.01~1.0重量份,更佳為0.03~0.8重量份,再更佳為0.05~0.5重量份。磷系穩定劑之含量介於上述範圍內時,係表現成形時之熱分解抑制效果,且機械特性之降低係變得不易發生。
(ii)酚系穩定劑
本發明之樹脂組成物可含有酚系穩定劑。作為酚系穩定劑,一般而言,可舉出受阻酚、半受阻酚、低受阻酚化合物,由對於聚碳酸酯樹脂施予熱穩定處理之觀點來看,特別適合使用受阻酚化合物。作為該受阻酚化合物,例如,可例示出α-生育酚、丁基羥基甲苯、芥子醇、維生素E、十八烷基-3-(3,5-二-tert-丁基-4-羥苯基)丙酸酯、2-tert-丁基-6-(3’-tert-丁基-5’-甲基-2’-羥基苄基)-4-甲基苯基丙烯酸酯、2,6-二-tert-丁基-4-(N,N-二甲基胺甲基)酚、3,5-二-tert-丁基-4-羥基苄基膦酸酯二乙基酯、2,2’-亞甲基雙(4-甲基-6-tert-丁基酚)、2,2’-亞甲基雙(4-乙基-6-tert-丁基酚)、4,4’-亞甲基雙(2,6-二-tert-丁基酚)、2,2’-亞甲基雙(4-甲基-6-環己基酚)、2,2’-二亞甲基-雙(6-α-甲基-苄基-p-甲酚)、2,2’-亞乙基-雙(4,6-二-tert-丁基酚)、2,2’-亞丁基-雙(4-甲基-6-tert-丁基酚)、4,4’-亞丁基雙(3-甲基-6-tert-丁基酚)、三乙二醇-N-雙-3-(3-tert-丁基-4-羥基-5-甲基苯基)丙酸酯、1,6-己二醇雙[3-(3,5-二-tert-丁基-4-羥苯基)丙酸酯]、雙[2-tert-丁基-4-甲基6-(3-tert-丁基-5-甲基-2-羥基苄基)苯基]對苯二甲酸酯、3,9-雙{2-[3-(3-tert-丁基-4-羥基-5-甲基苯基)丙醯氧基]-1,1-二甲基乙基}-2,4,8,10-四氧雜螺[5,5]十一烷、4,4’-硫代雙(6-tert-丁基-m-甲酚)、4,4’-硫代雙(3-甲基-6-tert-丁基酚)、2,2’-硫代雙(4-甲基-6-tert-丁基酚)、雙(3,5-二-tert-丁基-4-羥基苄基)硫醚、4,4’-二-硫代雙(2,6-二-tert-丁基酚)、4,4’-三-硫代雙(2,6-二-tert-丁基酚)、2,2-硫代二亞乙基雙-[3-(3,5-二-tert-丁基-4-羥苯基)丙酸酯]、2,4-雙(n-辛硫基)-6-(4-羥基-3,5-二-tert-丁基苯胺基)-1,3,5-三嗪、N,N’-六亞甲基雙-(3,5-二-tert-丁基-4-羥基氫化肉桂醯胺)、N,N’-雙[3-(3,5-二-tert-丁基-4-羥苯基)丙醯基]肼、1,1,3-三(2-甲基-4-羥基-5-tert-丁基苯基)丁烷、1,3,5-三甲基-2,4,6-三(3,5-二-tert-丁基-4-羥基苄基)苯、三(3,5-二-tert-丁基-4-羥苯基)異三聚氰酸酯、三(3,5-二-tert-丁基-4-羥基苄基)異三聚氰酸酯、1,3,5-三(4-tert-丁基-3-羥基-2,6-二甲基苄基)異三聚氰酸酯、1,3,5-三2[3(3,5-二-tert-丁基-4-羥苯基)丙醯氧基]乙基異三聚氰酸酯、四[亞甲基-3-(3,5-二-tert-丁基-4-羥苯基)丙酸酯]甲烷、三乙二醇-N-雙-3-(3-tert-丁基-4-羥基-5-甲基苯基)丙酸酯、三乙二醇-N-雙-3-(3-tert-丁基-4-羥基-5-甲基苯基)乙酸酯、3,9-雙[2-{3-(3-tert-丁基-4-羥基-5-甲基苯基)乙醯氧基}-1,1-二甲基乙基]-2,4,8,10-四氧雜螺[5,5]十一烷、四[亞甲基-3-(3-tert-丁基-4-羥基-5-甲基苯基)丙酸酯]甲烷、1,3,5-三甲基-2,4,6-三(3-tert-丁基-4-羥基-5-甲基苄基)苯,及三(3-tert-丁基-4-羥基-5-甲基苄基)異三聚氰酸酯等。上述化合物之中,較佳係使用四[亞甲基-3-(3-tert-丁基-4-羥基-5-甲基苯基)丙酸酯]甲烷、十八烷基-3-(3,5-二-tert-丁基-4-羥苯基)丙酸酯,此外作為抑制加工時之熱分解所引起之機械特性降低優異之物質,更佳係使用(3,3’,3”,5,5’,5”-六-tert-丁基-a,a’,a”-(均三甲苯基-2,4,6-三基)三-p-甲酚,及1,3,5-三-(3,5-二-tert-丁基-4-羥基苄基)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮。
上述酚系穩定劑係可單獨或將2種以上組合使用。酚系穩定劑之含量係相對於聚碳酸酯樹脂100重量份,較佳為0.05~1.0重量份,更佳為0.07~0.8重量份,再更佳為0.1~0.5重量份。酚系穩定劑之含量若介於上述範圍內,則表現成形時之熱分解抑制效果,且機械特性之降低係變得不易發生。
較佳係摻合磷系穩定劑及酚系穩定劑中之任一種,更佳係併用此等。併用之情況中,相對於聚碳酸酯樹脂100重量份,較佳係摻合0.01~0.5重量份之磷系穩定劑及0.01~0.5重量份之酚系穩定劑。
(iii)紫外線吸收劑
本發明之聚碳酸酯樹脂組成物係可含有紫外線吸收劑。作為紫外線吸收劑,在二苯甲酮系中,例如,可例示出2,4-二羥基二苯甲酮、2-羥基-4-甲氧基二苯甲酮、2-羥基-4-辛氧基二苯甲酮、2-羥基-4-苄氧基二苯甲酮、2-羥基-4-甲氧基-5-磺酸氧基二苯甲酮、2-羥基-4-甲氧基-5-磺酸氧基三水合物二苯甲酮、2,2’-二羥基-4-甲氧基二苯甲酮、2,2’,4,4’-四羥基二苯甲酮、2,2’-二羥基-4,4’-二甲氧基二苯甲酮、2,2’-二羥基-4,4’-二甲氧基-5-磺酸鈉二苯甲酮、雙(5-苯甲醯基-4-羥基-2-甲氧基苯基)甲烷、2-羥基-4-n-十二烷基氧基二苯甲酮,及2-羥基-4-甲氧基-2’-羧基二苯甲酮等。
苯并三唑系中,例如,可例示出2-(2-羥基-5-甲基苯基)苯并三唑、2-(2-羥基-5-tert-辛基苯基)苯并三唑、2-(2-羥基-3,5-二異丙苯基苯基)苯基苯并三唑、2-(2-羥基-3-tert-丁基-5-甲基苯基)-5-氯苯并三唑、2,2’-亞甲基雙[4-(1,1,3,3-四甲基丁基)-6-(2H-苯并三唑-2-基)酚]、2-(2-羥基-3,5-二-tert-丁基苯基)苯并三唑、2-(2-羥基-3,5-二-tert-丁基苯基)-5-氯苯并三唑、2-(2-羥基-3,5-二-tert-戊基苯基)苯并三唑、2-(2-羥基-5-tert-辛基苯基)苯并三唑、2-(2-羥基-5-tert-丁基苯基)苯并三唑、2-(2-羥基-4-辛氧基苯基)苯并三唑、2,2’-亞甲基雙(4-異丙苯基-6-苯并三唑苯基)、2,2’-p-伸苯基雙(1,3-苯并噁嗪-4-酮),及2-[2-羥基-3-(3,4,5,6-四氫鄰苯二甲醯亞胺甲基)-5-甲基苯基]苯并三唑,以及2-(2’-羥基-5-甲基丙烯醯氧基乙基苯基)-2H-苯并三唑和能夠與該單體共聚之乙烯系單體之共聚物或2-(2’-羥基-5-丙烯醯氧基乙基苯基)-2H-苯并三唑和能與該單體共聚之乙烯系單體之共聚物等的具有2-羥苯基-2H-苯并三唑骨架之聚合物等。
羥苯基三嗪系中,係可例示出例如,2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-己基氧基酚、2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-甲基氧基酚、2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-乙基氧基酚、2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-丙基氧基酚,及2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-丁基氧基酚等。此外可例示出2-(4,6-雙(2,4-二甲基苯基)-1,3,5-三嗪-2-基)-5-己基氧基酚等、上述例示化合物之苯基變成2,4-二甲基苯基之化合物。
環狀亞胺酯系中,可例示出例如2,2’-p-伸苯基雙(3,1-苯并噁嗪-4-酮)、2,2’-m-伸苯基雙(3,1-苯并噁嗪-4-酮),及2,2’-p,p’-二伸苯基雙(3,1-苯并噁嗪-4-酮)等。
氰基丙烯酸酯系中,可例示出例如1,3-雙-[(2’-氰基-3’,3’-二苯基丙烯醯基)氧基]-2,2-雙[(2-氰基-3,3-二苯基丙烯醯基)氧基]甲基)丙烷,及1,3-雙-[(2-氰基-3,3-二苯基丙烯醯基)氧基]苯等。
此外,上述紫外線吸收劑可以是透過採用能夠進行自由基聚合之單體化合物之結構而將該紫外線吸收性單體及/或光穩定性單體與(甲基)丙烯酸烷基酯等的單體進行共聚合而成之聚合物型之紫外線吸收劑。作為前述紫外線吸收性單體,較佳係可例示出(甲基)丙烯酸酯之酯取代基中含有苯并三唑骨架、二苯甲酮骨架、三嗪骨架、環狀亞胺酯骨架,及氰基丙烯酸酯骨架之化合物。
上述紫外線吸收劑係可單獨或將2種以上組合使用。
紫外線吸收劑之含量係相對於聚碳酸酯樹脂100重量份,較佳為0.1~10重量份,更佳為0.12~5重量份,再更佳為0.15~3重量份。紫外線吸收劑之含量若介於上述範圍內,則表現充分的耐光性,並防止成形時等之氣體產生所引起之外觀不良或物性低下故較佳。
(iv)受阻胺系光穩定劑
本發明之聚碳酸酯樹脂組成物可含有受阻胺系光穩定劑。受阻胺系光穩定劑一般被稱為HALS(Hindered Amine Light Stabilizer),為結構中具有2,2,6,6-四甲基哌啶骨架之化合物,例如,4-乙醯氧基-2,2,6,6-四甲基哌啶、4-丙烯醯氧基-2,2,6,6-四甲基哌啶、4-丙烯醯基氧基-2,2,6,6-四甲基哌啶、4-(苯基乙醯氧基)-2,2,6,6-四甲基哌啶、4-苯甲醯基氧基-2,2,6,6-四甲基哌啶、4-甲氧基-2,2,6,6-四甲基哌啶、4-硬脂氧基-2,2,6,6-四甲基哌啶、4-環己基氧基-2,2,6,6-四甲基哌啶、4-苄基氧基-2,2,6,6-四甲基哌啶、4-苯氧基-2,2,6,6-四甲基哌啶、4-(乙基胺基甲醯氧基)-2,2,6,6-四甲基哌啶、4-(環己基胺基甲醯氧基)-2,2,6,6-四甲基哌啶、4-(苯基胺基甲醯氧基)-2,2,6,6-四甲基哌啶、雙(2,2,6,6-四甲基-4-哌啶基)碳酸酯、雙(2,2,6,6-四甲基-4-哌啶基)草酸酯、雙(2,2,6,6-四甲基-4-哌啶基)丙二酸酯、雙(2,2,6,6-四甲基-4-哌啶基)癸二酸酯、雙(2,2,6,6-四甲基-4-哌啶基)己二酸酯、雙(2,2,6,6-四甲基-4-哌啶基)對苯二甲酸酯、雙(1,2,2,6,6-五甲基-4-哌啶基)碳酸酯、雙(1,2,2,6,6-五甲基-4-哌啶基)草酸酯、雙(1,2,2,6,6-五甲基-4-哌啶基)丙二酸酯、雙(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯、雙(1,2,2,6,6-五甲基-4-哌啶基)己二酸酯、雙(1,2,2,6,6-五甲基-4-哌啶基)對苯二甲酸酯、N,N’-雙-2,2,6,6-四甲基-4-六氫吡啶基-1,3-苯二甲醯胺、1,2-雙(2,2,6,6-四甲基-4-哌啶基氧基)乙烷、α,α’-雙(2,2,6,6-四甲基-4-哌啶基氧基)-p-二甲苯、雙(2,2,6,6-四甲基-4-哌啶基甲苯-2,4-二胺基甲酸酯、雙(2,2,6,6-四甲基-4-哌啶基)-六亞甲基-1,6-二胺基甲酸酯、三(2,2,6,6-四甲基-4-哌啶基)-苯-1,3,5-三羧酸酯、N,N’,N”,N”’-四-(4,6-雙-(丁基-(N-甲基-2,2,6,6-四甲基哌啶-4-基)胺)-三嗪-2-基)-4,7-二氮雜癸烷-1,10-二胺、二丁基胺・1,3,5-三嗪・N,N’-雙(2,2,6,6-四甲基-4-哌啶基)-1,6-六亞甲基二胺和N-(2,2,6,6-四甲基-4-哌啶基)丁基胺之聚縮合物、聚[{6-(1,1,3,3-四甲基丁基)胺-1,3,5-三嗪-2,4-二基}{(2,2,6,6-四甲基-4-哌啶基)亞胺}六亞甲基{(2,2,6,6-四甲基-4-哌啶基)亞胺}]、四(2,2,6,6-四甲基-4-哌啶基)-1,2,3,4-丁烷四羧酸酯、四(1,2,2,6,6-五甲基-4-哌啶基)-1,2,3,4-丁烷四羧酸酯、三(2,2,6,6-四甲基-4-哌啶基)-苯-1,3,4-三羧酸酯、1-[2-{3-(3,5-二-t-丁基-4-羥苯基)丙醯氧基}丁基]-4-[3-(3,5-二-t-丁基-4-羥苯基)丙醯氧基]2,2,6,6-四甲基哌啶,及1,2,3,4-丁烷四羧酸與1,2,2,6,6-五甲基-4-哌啶醇和β,β,β’,β’-四甲基-3,9-[2,4,8,10-四氧雜螺(5,5)十一烷]二乙醇之縮合物等。
受阻胺系光穩定劑係依據哌啶骨架中之氮原子的鍵結對象大致上分為N-H型(氫鍵結於氮原子上)、N-R型(烷基(R)鍵結於氮原子上)、N-OR型(烷氧基(OR)鍵結於氮原子上)之3種類型,然而用於聚碳酸酯樹脂時,由受阻胺系光穩定劑之鹼性之觀點來看,更佳係使用低鹼性之N-R型、N-OR型。
受阻胺系光穩定劑係可單獨或將2種以上組合使用。受阻胺系光穩定劑之含量相對於聚碳酸酯樹脂100重量份,較佳為0.01~2重量份,更佳為0.05~1重量份,再更佳為0.08~0.7重量份,特佳為0.1~0.5重量份。受阻胺系光穩定劑之含量若介於上述範圍內,則表現充分的耐光性,且由成形時等之氣體產生所引起之外觀不良或由聚碳酸酯樹脂之分解所引起之物性降低係受到抑制故較佳。
(v)其他之添加劑
其他,在本發明之聚碳酸酯樹脂組成物中,可以小比例摻合用於對成形品賦予各種機能或改善特性的其本身已知的添加物。此等添加物在不損害本發明之目的時,可為通常的摻合量。
作為該添加劑,可舉出滑動劑(例如PTFE粒子)、光擴散劑(例如丙烯酸交聯粒子、矽酮交聯粒子、極薄玻璃薄片、碳酸鈣粒子)、螢光染料、無機系螢光體(例如將鋁酸鹽作為母結晶之螢光體)、抗靜電劑、結晶核劑、無機及有機之抗菌劑、光觸媒系防汙劑(例如微粒子氧化鈦、微粒子氧化鋅)、自由基產生劑、紅外線吸收劑(熱線吸收劑),及光致變色劑等。
[實施例]
以下舉出實施例以進一步說明本發明。此外,除非另有說明否則實施例中之份為重量份、%為重量%。此外,評估係以下述之方法來實施。
(i)成形品外觀(設計性)
使用所獲得之顆粒,並以缸體溫度260℃、金型溫度60℃、射出速度30mm/s之條件,藉由射出成形來成形算術平均粗糙度(Ra)為0.03μm之厚度2mm之成形板(長度90mm×寬度50mm),觀察其成形品外觀(設計性)。
此外,確認成形品外觀有無點狀風格之設計性,確認到點狀風格的情況定為「〇」、雖確認到點狀風格然而亦觀察到金屬異物等不適於成形品外觀之情況係定為「×」、未確認到點狀風格之情況係表示為「××」。
(ii)阻燃性
使用以下述之方法所獲得之UL試驗片,依據UL94,實施V試驗。此外,判定為無法滿足V-0、V-1、V-2中之任一基準之情況,係顯示為「HB」。
[實施例1~4、比較例1~9]
以表1中所示之組成,進行將包含各成分之混合物分2階段供給至擠出機之供給口之方法。於各供給口添加混合物之混合機係使用V型摻合機、亨舍爾混合機及擠出混合機等的予備混合手段進行充分地混合。藉由第1供給口供給A成分、D~G成分之混合物,藉由第2供給口供給B成分與C成分之混合物,並以排氣式二軸擠出機進行熔融混練。擠出係使用直徑44mmφ之排氣式二軸擠出機((股)日本製鋼所TEX44αII-25AW-3V),並以螺旋旋轉數230rpm、吐出量150kg/h、排氣之真空度3kPa進行熔融混練獲得顆粒。此外,關於擠出溫度,自第1供給口至模具部分為止係以260℃實施。所獲得之顆粒的一部分係於80~100℃下藉由6小時熱風循環式乾燥機進行乾燥後,使用射出成形機,於缸體溫度250℃、金型溫度60℃成形UL試驗片。評估結果示於表2。此外,圖1係顯示由實施例1所獲得之顆粒以上述(i)之條件射出成形後之成形品之外觀。
此外,表1中之記號記載之各成分係如同下述。
(A成分)
A-1:芳香族聚碳酸酯樹脂(由雙酚A與光氣藉由常見方法製作之黏度平均分子量22,400之聚碳酸酯樹脂粉末、帝人(股)製Panlite L-1225WP(製品名))
(B成分)
B-1:包含著色劑之表面被覆矽酮系黏結劑樹脂之合成雲母粉
B-1-1;相對於表面被覆矽酮系黏結劑樹脂之合成雲母粉100%,包含二氧化鈦(石原產業製TIPAQUE PC-3)5.0%、碳黑(三菱製CB950)0.4%、黃色燒成顏料(Tokan Material Technology Co.,Ltd. 製42-118A)0.28%、紅色氧化鐵(Bayferrox公司製R180M)0.2%作為著色劑者,平均粒子徑500μm
B-1-2;相對於表面被覆矽酮系黏結劑樹脂之合成雲母粉100%,包含二氧化鈦(石原產業製TIPAQUE PC-3)5.0%、碳黑(三菱製CB950)0.05%、黃色燒成顏料(Tokan Material Technology Co.,Ltd. 製42-118A)0.1%、紅色氧化鐵(Bayferrox公司製R180M)0.2%作為著色劑者,平均粒子徑1000μm
B-2(比較):包含著色劑之表面被覆矽酮系黏結劑樹脂之天然雲母粉
B-2-1:相對於表面被覆矽酮系黏結劑樹脂之天然雲母粉100%,包含二氧化鈦(石原產業製TIPAQUE PC-3)5.0%、碳黑(三菱製CB950)0.4%、黃色燒成顏料(Tokan Material Technology Co.,Ltd. 製42-118A)0.28%、紅色氧化鐵(Bayferrox公司製R180M)0.2%作為著色劑者,平均粒子徑500μm
B-2-2:相對於表面被覆矽酮系黏結劑樹脂之天然雲母粉100%,包含二氧化鈦(石原產業製TIPAQUE PC-3)5.0%、碳黑(三菱製CB950)0.05%、黃色燒成顏料(Tokan Material Technology Co.,Ltd. 製42-118A)0.1%、紅色氧化鐵(Bayferrox公司製R180M)0.2%作為著色劑者,平均粒子徑1000μm
B-3(比較):包含著色劑之表面被覆環氧系黏結劑樹脂之合成雲母粉
B-3-1:相對於表面被覆環氧系黏結劑樹脂之合成雲母粉100%,包含二氧化鈦(石原產業製TIPAQUE PC-3)5.0%、碳黑(三菱製CB950)0.4%、黃色燒成顏料(Tokan Material Technology Co.,Ltd. 製42-118A)0.28%、紅色氧化鐵(Bayferrox公司製R180M)0.2%作為著色劑者,平均粒子徑500μm
B-3-2:相對於表面被覆環氧系黏結劑樹脂之合成雲母粉100%,包含二氧化鈦(石原產業製TIPAQUE PC-3)5.0%、碳黑(三菱製CB950)0.05%、黃色燒成顏料(Tokan Material Technology Co.,Ltd. 製42-118A)0.1%、紅色氧化鐵(Bayferrox公司製R180M)0.2%作為著色劑者,平均粒子徑1000μm
(C成分)
C-1:ABS-1:ABS樹脂[東麗製700-314(商品名)、丁二烯橡膠成分約12重量%、平均橡膠粒子徑為350nm]
(D成分)
D-1:滑石(林化成(股)製;HST0.8(商品名)、平均粒徑3.5μm)
D-2:矽灰石(清水工業(股)製;H-1250F(商品名)數量平均纖維直徑2.1μm、加權平均纖維長度26μm)
(E成分)
E-1:以雙酚A雙(二苯基磷酸酯)為主成分之磷酸酯(大八化學工業(股)製:CR-741(商品名))
(F成分)
F-1:PTFE(大金工業(股)製Polyflon MPA FA500H(商品名))
(G成分)
G-1:α-烯烴與馬來酸酐之共聚合產生之烯烴系蠟(三菱化學(股)製;DIACARNA 30M(商品名))
G-2:脂肪酸酯系脫模劑(理研維生素(股)製RIKEMAL SL900(製品名))
[產業上之可利用性]
本發明之聚碳酸酯樹脂組成物之成形品之外觀優良,進而由於由該樹脂組成物所形成之成形品具有設計性優良之點狀風格之外觀,故適宜作為OA機器領域、電子電氣機器領域等的外殼用材料使用,尤其作為行動電話或平板電腦等的殼體用途係為有用。
[圖1]為顯示出本發明之成形品中之點狀風格之外觀之一例之照片。
Claims (9)
- 一種聚碳酸酯樹脂組成物,其中,相對於(A)聚碳酸酯樹脂(A成分)100重量份,含有(B)表面以包含著色劑之矽酮系黏結劑樹脂被覆之合成雲母粉(B成分)0.01~8重量份。
- 如請求項1記載之聚碳酸酯樹脂組成物,其中,B成分之合成雲母粉之平均粒子徑為100~5000μm。
- 如請求項1記載之聚碳酸酯樹脂組成物,其中,相對於(A)聚碳酸酯樹脂(A成分)100重量份,含有(C)橡膠強化苯乙烯系樹脂(C成分)1~100重量份。
- 如請求項1記載之聚碳酸酯樹脂組成物,其中,相對於(A)聚碳酸酯樹脂(A成分)100重量份,含有(D)合成雲母粉以外之無機充填材(D成分)1~100重量份。
- 如請求項4記載之聚碳酸酯樹脂組成物,其中,D成分之無機充填材係由滑石及矽灰石所成之群所選出之至少1種無機充填劑。
- 如請求項1記載之聚碳酸酯樹脂組成物,其中,相對於(A)聚碳酸酯樹脂(A成分)100重量份,含有(E)阻燃劑(E成分)1~100重量份。
- 如請求項1記載之聚碳酸酯樹脂組成物,其中,相對於(A)聚碳酸酯樹脂(A成分)100重量份,含有(F)防滴落劑(F成分)0.01~10重量份。
- 如請求項1記載之聚碳酸酯樹脂組成物,其中,相對於(A)聚碳酸酯樹脂(A成分)100重量份,含有(G)脫模劑(G成分)0.01~10重量份。
- 一種具有點狀風格之外觀之成形品,其係由請求項1~8中之任一項所記載之聚碳酸酯樹脂組成物所形成。
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TW201229108A (en) * | 2010-10-20 | 2012-07-16 | Mitsubishi Chem Corp | Photoluminescent resin composition and decorated sheet |
JP2013089866A (ja) * | 2011-10-20 | 2013-05-13 | Teijin Chem Ltd | 遮熱性屋外設置用ポリカーボネート樹脂筐体 |
US20170167807A1 (en) * | 2015-12-14 | 2017-06-15 | Industrial Technology Research Institute | Heat shielding material, heat shielding composition and heat shielding structure employing the same |
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TW201229108A (en) * | 2010-10-20 | 2012-07-16 | Mitsubishi Chem Corp | Photoluminescent resin composition and decorated sheet |
JP2013089866A (ja) * | 2011-10-20 | 2013-05-13 | Teijin Chem Ltd | 遮熱性屋外設置用ポリカーボネート樹脂筐体 |
US20170167807A1 (en) * | 2015-12-14 | 2017-06-15 | Industrial Technology Research Institute | Heat shielding material, heat shielding composition and heat shielding structure employing the same |
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