TWI687472B - 樹脂用改質劑及使用其之樹脂組成物 - Google Patents
樹脂用改質劑及使用其之樹脂組成物 Download PDFInfo
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- TWI687472B TWI687472B TW105110110A TW105110110A TWI687472B TW I687472 B TWI687472 B TW I687472B TW 105110110 A TW105110110 A TW 105110110A TW 105110110 A TW105110110 A TW 105110110A TW I687472 B TWI687472 B TW I687472B
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- BGNTUSKZDOUZCZ-UHFFFAOYSA-N tris(1-butoxyethyl) phosphate Chemical compound CCCCOC(C)OP(=O)(OC(C)OCCCC)OC(C)OCCCC BGNTUSKZDOUZCZ-UHFFFAOYSA-N 0.000 description 1
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08L1/02—Cellulose; Modified cellulose
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- C08L1/14—Mixed esters, e.g. cellulose acetate-butyrate
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- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
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Abstract
Description
本發明係關於樹脂用改質劑(以下亦僅稱為「改質劑」)及使用其之樹脂組成物,詳細而言,係關於可對樹脂賦予優異的防濕性、尺寸穩定性、光學特性之樹脂用改質劑及使用其之樹脂組成物。
近年來,醯化纖維素、聚碳酸酯、聚丙烯酸酯、聚烯烴等之樹脂薄膜,主要用於液晶顯示裝置用偏光板保護薄膜或光學補償薄膜。當中,醯化纖維素薄膜,由於對用於偏光件之聚乙烯醇的貼合性優異之點,透明度高,且具有適度的強度,故被廣泛地使用。
然而,醯化纖維素薄膜,由於透濕性高,而有因外部濕氣的穿透,導致從偏光件的剝離或偏光件本身的劣化之缺失。此外,高溫高濕下,關於因吸濕所導致之偏光板保護薄膜或光學補償薄膜的收縮(尺寸穩定性),或是對觀看性有所影響之相位差變動(光學特性),仍存在著課題。近年來,伴隨著液晶顯示裝置的薄型化,偏光板保護薄膜或光學補償薄膜的薄型化亦隨之進行,因而要
求更高度的防濕性、尺寸穩定性及光學特性。
對於此問題,專利文獻1中,係提出一種對由纖維素酯樹脂所構成之薄膜賦予高遲滯值,不含芳香環,並且由以二元醇與二質子酸所構成之聚酯而組成之纖維素酯樹脂用添加劑。此外,專利文獻2中,係提出一種由高溫多濕下的耐滲出性優異,且於製造步驟中不易揮發之酯化合物所構成之纖維素酯樹脂用添加劑。
專利文獻1:日本WO2007/000910號公報
專利文獻2:日本特開2010-248493號公報
然而,專利文獻1中,雖揭示透濕度小者較佳,但並未探討具體的改善方式。此外,專利文獻2中,並未探討尺寸穩定性,且關於透濕度,亦無可充分滿足性能者。有鑑於此,至目前為止仍未發現到皆可滿足防濕性、尺寸穩定性、光學特性之改質劑。
因此,本發明之目的在於提供一種可對樹脂賦予優異的防濕性、尺寸穩定性、光學特性之樹脂用改質劑及使用其之樹脂組成物。
本發明者們係為了解決上述課題而進行精心探討,結果發現藉由使用具有下述結構之化合物作為樹脂用改質劑,可解決上述課題,因而完成本發明。
(式(1)中,m表示1~5的整數,n表示0~50的整數,RA、RB及RC表示碳原子數2~20的烴基,或是具有選自由氧原子、硫原子、氮原子所組成之群組之1個以上的原子之碳原子數2~20的烴基)。
本發明之樹脂用改質劑中,以前述一般式(1)所示之化合物之RA、RB及RC,較佳為碳原子數2~12的烴基,或是具有選自由氧原子、硫原子、氮原子所組成之群組之1個以上的原子之碳原子數2~12的烴基。此外,本發明之樹脂用改質劑,係適合用於熱塑性樹脂,尤其適合於纖維素系樹脂。
本發明之樹脂組成物,其特徵為含有本發明之樹脂用改質劑。
根據本發明,可提供一種可對樹脂賦予優異
的防濕性、尺寸穩定性、光學特性之樹脂用改質劑及使用其之樹脂組成物。
以下係詳細說明本發明之實施形態。
可對樹脂賦予優異的防濕性、尺寸穩定性、光學特性。在此,上述式(1)中,m為1~5的整數,較佳為1~3,尤佳為1。m為3時,較佳於芳香環上的3位、4位、5位上具有羥基,m為2時,較佳於芳香環上的3位、5位上具有羥基,m為1時,較佳於芳香環上的4位上具有羥基。
此外,上述式(1)中,n為0~50的整數,較佳為0~30,尤佳為0~20。本發明之樹脂用改質劑的製造方法並無特別限定,例如可將琥珀酸、對苯二甲酸等之二價的酸成分、此等酸成分的酐及此等酸的氯化物、乙二醇、丙二醇等之二醇成分、對羥基苯甲酸等之一價的酸成分,在觸媒存在下或無觸媒下一次或分批地投入,進行酯化反應或酯交換反應,然後進行一般方法的後續處理而得到以一般式(1)所示之化合物。
此時,所得之化合物具有分子量分布。本發明之樹脂用改質劑,可為具有分子量分布之化合物的混合物,或是藉由蒸餾等來精製此等之單一品,從經濟性之觀點來看,較佳為具有分子量分布之化合物的混合物。為具有分子量分布之化合物的混合物時,由於透濕性與光學特性(相位差變動值)優異,所以在n為0之化合物中,以一般式(1)所示之化合物中,較佳係含有0~80質量%,尤佳係含有5~75質量%,更佳係含有10~60質量%。
本發明之樹脂用改質劑中,式(1)中,以RA、RB及RC所示之碳原子數2~20,較佳為2~12的烴基,例如可列舉出碳原子數2~20之直鏈狀或分枝狀的伸烷基、碳原子數2~20之直鏈狀或分枝狀的伸烯基、可具有直鏈狀或分枝狀的取代基之環伸烷基、可具有直鏈狀或分枝狀的取代基之伸芳基等,取代基,表示烷基或伸烷基。
當中,較佳為直鏈狀或分枝狀的伸烷基或伸芳基,尤佳為碳原子數2~12之直鏈狀或分枝狀的伸烷基或伸芳基,更佳為伸乙基、伸正丙基、伸異丙基、伸正丁基、伸異丁基、伸正戊基、伸異戊基、伸正己基、伸異己基、伸正庚基、伸異庚基、伸正辛基、伸異辛基、伸正壬基、伸異壬基、伸正癸基、伸異癸基、伸正十一烷基、伸異十一烷基、伸正十二烷基、伸異十二烷基、伸苯基、伸萘基,最佳為伸乙基、伸正丙基、伸異丙基、伸正丁基、伸異丁基。
本發明之樹脂用改質劑中,式(1)中,RA、RB及RC的烴基,可藉由選自由氧原子、硫原子、氮原子所組成之群組之1個以上的原子所取代,碳原子數2~20,較佳為2~12的烴基,可列舉出以具有氧原子、硫原子、氮原子之取代基來取代1個以上的氫原子之情形,或是以氧原子、硫原子、氮原子來取代1個以上的碳原子之情形。
以具有氧原子、硫原子、氮原子之取代基來取代1個以上的氫原子時,例如可列舉出羥基、烷氧基、芳氧基、醯基、羰基、羧基等。
以氧原子、硫原子、氮原子來取代1個以上的碳原子時,例如可列舉出醚鍵、硫化鍵、胺鍵等。RA及RC較佳為二乙醚-1,1'-二基。此外,RB較佳為伸乙基、伸正丙基、伸苯基。具有n個之RA、RB及RC,可為相同或相異。
本發明之樹脂用改質劑中,分子量並無特別限定,從對樹脂之相溶性或防濕性能之觀點來看,數量平均分子量較佳為350~5,000,尤佳為350~2,000,更佳為350~1,500。數量平均分子量,可使用凝膠滲透層析法(GPC:Gel Permeation Chromatography)來測定。
本發明之樹脂用改質劑的調配量並無特別限定,相對於樹脂100質量份,為0.1~100質量份,較佳為0.5~80質量份,尤佳為1~50質量份,更佳為1~30質量份。未達0.1質量份時,有時無法充分地發揮防濕性、尺
寸穩定性、光學特性(相位差變動值)等性能,多於100質量份時,有時會滲出。
以下係例示出本發明之以一般式(1)所示之樹脂用改質劑,但本發明並不限定於此。此外,樹脂用改質劑A~Q的括弧內表示莫耳比,此等化合物可單獨使用或併用2種以上。
改質劑A:由琥珀酸(95)/對苯二甲酸(5)/1,2-丙二醇(100)所構成之縮合物的兩末端之對羥基苯甲酸酯物(數量平均分子量:880、n為0之化合物的比率:15質量%)
改質劑B:由琥珀酸(50)/對苯二甲酸(50)/1,2-丙二醇(100)所構成之縮合物的兩末端之對羥基苯甲酸酯物(數量平均分子量:880、n為0之化合物的比率:15質量%)
改質劑C:由琥珀酸(50)/對苯二甲酸(50)/1,2-丙二醇(100)所構成之縮合物的兩末端之對羥基苯甲酸酯物(數量平均分子量:650、n為0之化合物的比率:20質量%)
改質劑D:由琥珀酸(50)/對苯二甲酸(50)/乙二醇(100)所構成之縮合物的兩末端之對羥基苯甲酸酯物(數量平均分子量:570、n為0之化合物的比率:23質量%)
改質劑E:由琥珀酸(30)/對苯二甲酸(70)/1,2-丙
二醇(100)所構成之縮合物的兩末端之對羥基苯甲酸酯物(數量平均分子量:740、n為0之化合物的比率:17質量%)
改質劑F:由琥珀酸(30)/對苯二甲酸(70)/1,3-丁二醇(100)所構成之縮合物的兩末端之對羥基苯甲酸酯物(數量平均分子量:660、n為0之化合物的比率:20質量%)
改質劑G:由琥珀酸(5)/對苯二甲酸(95)/1,2-丙二醇(100)所構成之縮合物的兩末端之對羥基苯甲酸酯物(數量平均分子量:1190、n為0之化合物的比率:10質量%)
改質劑H:由琥珀酸(100)/1,2-丙二醇(100)所構成之縮合物的兩末端之對羥基苯甲酸酯物(數量平均分子量:650、n為0之化合物的比率:29質量%)
改質劑I:由對苯二甲酸(100)/1,3-丁二醇(100)所構成之縮合物的兩末端之對羥基苯甲酸酯物(數量平均分子量:700、n為0之化合物的比率:23質量%)
改質劑J:由琥珀酸(50)/對苯二甲酸(50)/乙二醇(50)/1,2-丙二醇(50)所構成之縮合物的兩末端之對羥基苯甲酸酯物(數量平均分子量:550、n為0之化合物的比率:24質量%)
改質劑K:由琥珀酸(50)/對苯二甲酸(50)/1,3-丁二醇(100)所構成之縮合物的兩末端之對羥基苯甲酸酯物(數量平均分子量:670、n為0之化合物的比率:
27質量%)
改質劑L:由鄰苯二甲酸(100)/1,2-丙二醇(100)所構成之縮合物的兩末端之對羥基苯甲酸酯物(數量平均分子量:640、n為0之化合物的比率:30質量%)
改質劑M:由對苯二甲酸(100)/1,2-丙二醇(100)所構成之縮合物的兩末端之對羥基苯甲酸酯物(數量平均分子量:640、n為0之化合物的比率:24質量%)
改質劑N:由琥珀酸(50)/對苯二甲酸(50)/1,2-丙二醇(100)所構成之縮合物的兩末端之對羥基苯甲酸酯物(數量平均分子量:490、n為0之化合物的比率:39質量%)
改質劑O:由琥珀酸(50)/對苯二甲酸(50)/乙二醇(10)/二乙二醇(90)所構成之縮合物的兩末端之對羥基苯甲酸酯物(數量平均分子量:410、n為0之化合物的比率:51質量%)
改質劑P:由對苯二甲酸(100)/乙二醇(100)所構成之縮合物的兩末端之對羥基苯甲酸酯物(數量平均分子量:370、n為0之化合物的比率:39質量%)
改質劑Q:由琥珀酸(50)/對苯二甲酸(50)/1,6-己二醇(100)所構成之縮合物的兩末端之對羥基苯甲酸酯物(數量平均分子量:390、n為0之化合物的比率:54質量%)
接著說明本發明之樹脂組成物。本發明之樹脂組成物,係含有本發明之樹脂用改質劑,且具有優異的
防濕性、尺寸穩定性、光學特性。本發明之樹脂組成物所使用之樹脂並無特別限定,例如可列舉出熱塑性樹脂、熱硬化性樹脂,可較佳地使用熱塑性樹脂。
熱塑性樹脂,例如可列舉出聚氯乙烯樹脂、聚乙烯樹脂、聚丙烯樹脂、聚苯乙烯樹脂、聚乙酸乙烯酯樹脂、聚胺甲酸酯樹脂、纖維素系樹脂、丙烯酸樹脂、AS(丙烯腈-苯乙烯)樹脂、ABS(丙烯腈-丁二烯-苯乙烯)樹脂、氟系樹脂、熱塑性彈性體、聚醯胺樹脂、聚縮醛樹脂、聚碳酸酯樹脂、改質聚苯醚樹脂、聚對苯二甲酸乙二酯樹脂、聚對苯二甲酸丁二酯樹脂、聚乳酸系樹脂、環狀聚烯烴樹脂、聚苯硫醚樹脂等,此等樹脂可單獨使用或組合2種以上使用。
聚氯乙烯樹脂,例如可列舉出聚氯乙烯、聚偏二氯乙烯等之均聚物、氯乙烯或偏二氯乙烯與乙酸乙烯酯之共聚物等之乙烯系化合物共聚物等。此等可單獨使用或組合2種以上使用。
聚乙烯樹脂,例如可列舉出低密度聚乙烯、中密度聚乙烯、高密度聚乙烯等。此等可單獨使用或組合2種以上使用。
聚丙烯樹脂,該聚合方法並無特別限定,例如可列舉出均聚物、隨機聚合物、嵌段聚合物等,此等可單獨使用或組合2種以上使用。
纖維素系樹脂,例如可列舉出賽珞凡(Cellophane)、賽璐珞(Celluloid)、纖維素乙酸酯、
纖維素二乙酸酯、纖維素三乙酸酯、纖維素丙酸酯、纖維素乙酸丙酸酯、纖維素乙酸丁酸酯、乙酸甲酯、乙基纖維素、羧甲基纖維素、羥乙基纖維素、羥丙基纖維素、乙基羥乙基纖維素、羧甲基乙基纖維素等。此等可單獨使用或組合2種以上使用。
丙烯酸樹脂,例如可列舉出聚丙烯酸甲酯、聚甲基丙烯酸甲酯等。此等可單獨使用或組合2種以上使用。
聚醯胺樹脂,例如可列舉出尼龍-6、尼龍-66、尼龍-10、尼龍-12、尼龍-46等之脂肪族聚醯胺、藉由芳香族二羧酸與脂肪族二胺所製造之芳香族聚醯胺等。此等可單獨使用或組合2種以上使用。
聚縮醛樹脂,例如可列舉出聚甲醛、聚乙醛、聚丙醛、聚丁醛等。此等可單獨使用或組合2種以上使用。
此等當中,尤佳為纖維素系樹脂,更佳為纖維素的低級脂肪酸酯。纖維素的低級脂肪酸酯中的低級脂肪酸,意指碳原子數為6以下之脂肪酸。纖維素的低級脂肪酸酯,例如可列舉出纖維素乙酸酯、纖維素丙酸酯、纖維素丁酸酯等,或是日本特開平10-45804號公報、日本特開平8-231761號公報、美國專利第2,319,052號說明書等所記載之纖維素乙酸丙酸酯、纖維素乙酸丁酸酯等之混合脂肪酸酯。
本發明之樹脂組成物中,除了本發明之樹脂
用改質劑之外,亦可調配可塑劑,以及各種添加劑,例如酚系或硫系抗氧化劑、紫外線吸收劑、受阻胺系光穩定劑、多元醇類、其他無機化合物等。此等可塑劑或各種添加劑,可單獨使用或併用2種以上。
可塑劑,例如可列舉出鄰苯二甲酸二丁酯、鄰苯二甲酸丁基己酯、鄰苯二甲酸二庚酯、鄰苯二甲酸二(2-乙基己基)酯、鄰苯二甲酸二異壬酯、鄰苯二甲酸二異癸酯、鄰苯二甲酸二月桂酯、鄰苯二甲酸二環己酯、鄰苯二甲酸二辛酯等之鄰苯二甲酸酯系可塑劑;己二酸二辛酯、己二酸二異壬酯、己二酸二異癸酯、己二酸二(丁基二甘醇)酯等之己二酸酯系可塑劑;磷酸三苯酯、磷酸三甲酚酯、磷酸三甲苯酯、磷酸三(異丙基苯基)酯、磷酸三乙酯、磷酸三丁酯、磷酸三辛酯、磷酸三(丁氧基乙基)酯、磷酸辛基二苯酯等之磷酸酯系可塑劑;使用乙二醇、二乙二醇、三乙二醇、1,3-丁二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、新戊二醇、三羥甲基丙烷等之多元醇,與草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、肉桂酸等之二質子酸,且因應必要使用一元醇、單羧酸(乙酸、芳香族酸等)作為停止劑之本發明以外的聚酯系可塑劑;環氧化大豆油、環氧化亞麻仁油、環氧化桐油、環氧化魚油、環氧化牛脂油、環氧化蓖麻油、環氧化葵花油、環氧化硬脂酸甲酯、環氧化硬脂酸丁酯、環氧化硬脂酸2-乙基己酯、環氧化硬脂酸硬脂酯、
環氧化聚丁二烯、異三聚氰酸三(環氧基丙基)酯、環氧化松油脂肪酸酯、環氧化亞麻仁油脂肪酸酯、雙酚A二縮水甘油醚、二環氧化乙烯基環己烯、二環氧化二環己烯、3,4-環氧基環己基甲基、環氧環己烷羧酸酯等之環氧系可塑劑;其他可列舉出四氫鄰苯二甲酸系可塑劑、壬二酸系可塑劑、癸二酸二(2-乙基己酯基)酯(DOS)、癸二酸二丁酯(DBS)等之癸二酸系可塑劑、硬脂酸系可塑劑、檸檬酸系可塑劑、焦蜜石酸系可塑劑、聯苯聚羧酸系可塑劑、多元醇的芳香族酸酯系可塑劑(三羥甲基丙烷的苄酸酯等)等。較佳可列舉出本發明以外的聚酯系可塑劑、鄰苯二甲酸酯系可塑劑、偏苯三甲酸酯系可塑劑、己二酸酯系可塑劑、癸二酸系可塑劑、環氧系可塑劑。
本發明之樹脂用改質劑以外之聚酯系可塑劑的具體化合物,係例示於可塑劑1~13,但並不限定於此等,此等化合物可單獨使用或使用2種以上作為混合物。
下述可塑劑1~4的括弧內表示莫耳比,此等聚酯系可塑劑可單獨使用或使用2種以上作為混合物。
可塑劑-1:下述一般式(2)之由作為多元醇成分G的乙二醇(50)及1,2-丙二醇(50)、作為多元羧酸成分A的琥珀酸(50)及對苯二甲酸(50)、以及末端E為乙醯基所構成之n=5的化合物。
可塑劑-2:上述一般式(2)之由作為多元醇成分G
的1,2-丙二醇、作為多元羧酸成分A的2,6-萘二羧酸、以及末端E為氫所構成之n=2的化合物。
可塑劑-3:上述一般式(2)之由作為多元醇成分G的乙二醇、作為多元羧酸成分A的己二酸、以及末端E為乙醯基所構成之n=10的化合物。
可塑劑-4:上述一般式(2)之由作為多元醇成分G的1,2-丙二醇、作為多元羧酸成分A的對苯二甲酸、以及末端E為甲苯基所構成之n=5的化合物。
可塑劑-5:下述一般式(3)之取代基QA皆為氫原子之化合物。
可塑劑-6:上述一般式(3)之取代基QA皆為甲氧基之化合物。
此等可塑劑的含量,可在不損及本發明的效果之範圍內調配,相對於樹脂100質量份,較佳為1~90質量份,尤佳為10~80質量份。
酚系抗氧化劑,例如可列舉出2,6-二(三級丁基)對甲酚、2,6-二苯基-4-十八烷氧基酚、硬脂基(3,5-二(三級丁基)-4-羥苯基)丙酸酯、二硬脂基(3,5-二(三級丁基)-4-羥苄基)膦酸酯、十三烷基-3,5-二(三級丁基)-4-羥苄基硫代乙酸酯、硫代二乙烯雙[(3,5-二(三級丁基)-4-羥苯基)丙酸酯]、4,4'-硫代雙(6-三級丁基間甲酚)、2-辛基硫-4,6-二(3,5-二(三級丁基)-4-羥苯氧基)-s-三嗪、2,2'-亞甲雙(4-甲基-6-三級丁基酚)、雙[3,3-雙(4-羥基-3-三級丁基苯基)丁酸]二醇酯、4,4'-亞丁基雙(4,6-二(三級丁基)酚)、2,2'-亞乙基雙(4,6-二(三級丁基)酚)、1,1,3-三(2-甲基-4-羥基-5-三級丁基苯基)丁烷、雙[2-三級丁基-4-甲基-6-(2-羥基-3-三級丁基-5-甲基苄基)苯基]對苯二甲酸酯、
1,3,5-三(2,6-二甲基-3-羥基-4-三級丁基苄基)異三聚氰酸酯、1,3,5-三(3,5-二(三級丁基)-4-羥苄基)異三聚氰酸酯、1,3,5-三(3,5-二(三級丁基)-4-羥苄基)-2,4,6-三甲基苯、1,3,5-三[(3,5-二(三級丁基)-4-羥苯基)丙醯氧基乙基]異三聚氰酸酯、四[亞甲基-3-(3,5-二(三級丁基)-4-羥苯基)丙酸酯]甲烷、二(三級丁基)-4-甲基-6-(2-丙烯醯氧基-3-三級丁基-5-甲基苄基)酚、3,9-雙[2-{3-(3-三級丁基-4-羥基-5-甲基苯基)丙醯氧基}-1,1-二甲基乙基]-2,4,8,10-四噁螺旋[5.5]十一烷、三乙二醇三[β-(3-三級丁基-4-羥基-5-甲基苯基)丙酸酯]等。此等酚系抗氧化劑的含量,可在不損及本發明的效果之範圍內調配,相對於樹脂100質量份,較佳為0.01~1質量份,尤佳為0.03~0.8質量份。
硫系抗氧化劑,例如可列舉出硫代二丙酸的二月桂酯、二肉豆蔻酯、肉豆蔻硬脂酯、二硬脂酯等之二烷基硫代二丙酸酯類以及新戊四醇四(β-十二烷基巰基丙酸酯)等之多元醇的β-烷基巰基丙酸酯類等。此等硫系抗氧化劑的含量,可在不損及本發明的效果之範圍內調配,相對於樹脂100質量份,較佳為0.01~1質量份,尤佳為0.03~0.8質量份。
紫外線吸收劑,例如可列舉出2,4-二羥基二苯基酮、2-羥基-4-甲氧基二苯基酮、2-羥基-4-辛氧基二苯基酮、2-羥基-4-三級丁基-4'-(2-甲基丙烯醯氧基乙氧乙氧基)二苯基酮、5,5'-亞甲基雙(2-羥基-4-甲氧基二苯
基酮)等之2-羥基二苯基酮類;2-(2-羥基-5-甲基苯基)苯并三唑、2-(2-羥基-5-三級辛基苯基)苯并三唑、2-(2-羥基-3,5-二(三級丁基)苯基)-5-氯苯并三唑、2-(2-羥基-3-三級丁基-5-甲基苯基)-5-氯苯并三唑、2-(2-羥基-3-十二烷基-5-甲基苯基)苯并三唑、2-(2-羥基-3-三級丁基-5-C7~9混合烷氧羰基乙基苯基)三唑、2-(2-羥基-3,5-二異丙苯基苯基)苯并三唑、2,2'-亞甲基雙(4-三級辛基-6-苯并三唑酚)、2-(2-羥基-3-三級丁基-5-羥苯基)苯并三唑的聚乙二醇酯等2-(2-羥苯基)苯并三唑類;2-(2-羥基-4-己氧基苯基)-4,6-二苯基-1,3,5-三嗪、2-(2-羥基-4-甲氧基苯基)-4,6-二苯基-1,3,5-三嗪、2-(2-羥基-4-辛氧基苯基)-4,6-雙(2,4-二甲基苯基)-1,3,5-三嗪、2-(2-羥基-4-丙烯醯氧基乙氧基苯基)-4,6-雙(2,4-二甲基苯基)-1,3,5-三嗪、2-(2-羥基-4-(2-(2-乙基己醯氧基)乙氧基)苯基)-4,6-二苯基-1,3,5-三嗪、2,4,6-三(2-羥基-4-辛氧基苯基)-1,3,5-三嗪、2,4,6-三(2-羥基-3-甲基-4-(2-辛醯氧基乙基)苯基)-1,3,5-三嗪等之2-(2-羥苯基)-1,3,5-三嗪類;柳酸苯酯、間苯二酚單苄酸酯、2,4-二(三級丁基)苯基-3,5-二(三級丁基)-4-羥基苄酸酯、2,4-二(三級戊基)苯基-3,5-二(三級丁基)-4-羥基苄酸酯、十六烷基-3,5-二(三級丁基)-4-羥基苄酸酯等之苄酸酯類;2-乙基-2'-乙氧基草醯苯胺、2-乙氧基-4'-十二烷基草醯苯胺等之取代草醯苯胺類;乙基-α-氰基-β,β-二苯基丙烯酸酯、甲基-2-氰基-
3-甲基-3-(對甲氧基苯基)丙烯酸酯、四(α-氰基-β,β-二苯基丙烯醯氧基甲基)甲烷等之氰基丙烯酸酯類等。此等紫外線吸收劑的含量,可在不損及本發明的效果之範圍內調配,相對於樹脂100質量份,較佳為0.01~5質量份,尤佳為0.03~3質量份。
受阻胺系光穩定劑,例如可列舉出2,2,6,6-四甲基-4-哌啶基硬脂酸酯、1,2,2,6,6-五甲基-4-哌啶基硬脂酸酯、2,2,6,6-四甲基-4-哌啶基苄酸酯、雙(2,2,6,6-四甲基-4-哌啶基)癸二酸酯、雙(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯、雙(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)癸二酸酯、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、雙(2,2,6,6-四甲基-4-哌啶基)-雙(十三烷基)-1,2,3,4-丁烷四羧酸酯、雙(1,2,2,6,6-五甲基-4-哌啶基)-雙(十三烷基)-1,2,3,4-丁烷四羧酸酯、雙(1,2,2,6,6-五甲基-4-哌啶基)-2-丁基-2-(3,5-二(三級丁基)-4-羥苄基)丙二酸酯、1-(2-羥乙基)-2,2,6,6-四甲基-4-哌啶醇/琥珀酸二乙酯聚縮合物、1,6-雙(2,2,6,6-四甲基-4-哌啶基胺基)己烷/二溴乙醇聚縮合物、1,6-雙(2,2,6,6-四甲基-4-哌啶基胺基)己烷/2,4-二氯-6-嗎啉基-s-三嗪聚縮合物、1,6-雙(2,2,6,6-四甲基-4-哌啶基胺基)己烷/2,4-二氯-6-三級辛基胺基-s-三嗪聚縮合物、1,5,8,12-四[2,4-雙(N-丁基-N-(2,2,6,6-四甲基-4-哌啶基)胺基)-s-三嗪-6-基]-1,5,8,12-四氮雜十二烷、1,5,8,12-四[2,4-雙(N-丁
基-N-(1,2,2,6,6-五甲基-4-哌啶基)胺基)-s-三嗪-6-基]-1,5,8,12-四氮雜十二烷、1,6,11-三[2,4-雙(N-丁基-N-(2,2,6,6-四甲基-4-哌啶基)胺基-s-三嗪-6-基胺基]十一烷、1,6,11-三[2,4-雙(N-丁基-N-(1,2,2,6,6-五甲基-4-哌啶基)胺基-s-三嗪-6-基胺基]十一烷、3,9-雙[1,1-二甲基-2-{三(2,2,6,6-四甲基-4-哌啶氧基羰基)丁基羰氧基}乙基]-2,4,8,10-四噁螺旋[5.5]十一烷、3,9-雙[1,1-二甲基-2-{三(1,2,2,6,6-五甲基-4-哌啶氧基羰基)丁基羰氧基}乙基]-2,4,8,10-四噁螺旋[5.5]十一烷、雙(1-十一烷氧基-2,2,6,6-四甲基哌啶基-4-基)碳酸酯等。此等受阻胺系光穩定劑的含量,可在不損及本發明的效果之範圍內調配,相對於樹脂100質量份,較佳為0.01~1質量份,尤佳為0.03~0.8質量份。
多元醇類,例如可列舉出三羥甲基丙烷、二(三羥甲基)丙烷、新戊四醇、二新戊四醇、聚新戊四醇、新戊四醇或二新戊四醇的硬脂酸半酯、己二酸雙(二新戊四醇)酯、甘油、異三聚氰酸三(2-羥乙基)酯、山梨醇、甘露糖醇、乳糖醇等。此等多元醇類的含量,可在不損及本發明的效果之範圍內調配,相對於樹脂100質量份,較佳為0.01~2質量份,尤佳為0.01~1質量份。
其他無機化合物,例如可列舉出矽酸鈣、磷酸鈣、氧化鈣、氫氧化鈣、矽酸鎂、磷酸鎂、氧化鎂、氫氧化鎂等。其他無機化合物的含量,可在不損及本發明的效果之範圍內調配,相對於樹脂100質量份,較佳為
0.01~5質量份,尤佳為0.03~3質量份。
其他,本發明之樹脂組成物中,可因應必要,在不損及本發明的效果之範圍內,進一步調配其他添加劑,例如充填劑、著色劑、交聯劑、抗帶電劑、防霧劑、防滲出劑、表面處理劑、潤滑劑、難燃劑、螢光劑、防黴劑、殺菌劑、金屬非活化劑、脫模劑、顏料、加工輔助劑、發泡劑、有機酸金屬鹽、菱水鎂鋁石(Hydrotalcite)化合物、鋅改質菱水鎂鋁石、沸石化合物等。
本發明之樹脂組成物,其特徵為含有以上述一般式(1)所示之樹脂用改質劑,該調配方法及成形方法並無特別限定,調配方法,可列舉出以通常的摻合機、混合機等來混合之方法、以擠壓機等進行熔融混練之方法、與溶劑一同混合並進行溶液澆注之方法等,成形方法,可列舉出擠壓成形、射出成形、拉伸薄膜成形、吹出成形等。
使本發明之樹脂組成物成形所得之成形體的形狀並無特別限定,例如可列舉出薄片狀、薄膜狀、特殊形狀等。
所得之成形體的用途並無特別限定,例如可列舉出食品容器、電子零件、汽車零件、醫療用材料、薄膜-薄片材料、纖維材料、光學材料、塗料用樹脂、油墨用樹脂、色劑用樹脂、接著劑用樹脂等。
以下藉由實施例來更詳細說明本發明。惟本發明並不受限於以下實施例。
使用下述第1表及第2表所示之樹脂用改質劑,依循下述步驟來評估防濕性(透濕度)、光學特性(相位差變動值)及尺寸穩定性。並於同一表中一同記載所得之結果。數量平均分子量的測定,係依據下述步驟來進行。
將本發明之樹脂用改質劑A~Q或比較化合物1~14溶解於四氫呋喃(THF),調製出0.5質量%的樣本溶液,使用凝膠滲透層析法(GPC)並於下述條件下測定數量平均分子量。檢量線,係使用聚苯乙烯(GL Sciences公司製之分子量標準:分子量162、370、580、1000、2000、3000、5000)來製作。管柱,係使用昭和電工股份有限公司製SHODEX KF-802。管柱溫度設為40℃,溶離液使用THF,流量設為1ml/分,檢測器係使用折射率計(RI)來測定。
將纖維素三乙酸酯85質量份(乙醯化度61%、聚合度260)及改質劑15質量份,一邊攪拌一邊均一地溶解
於由二氯甲烷900質量份與甲醇100質量份所構成之混合溶劑,調製出各種評估用及薄膜製作用摻雜液。接著將所得之摻雜液澆注於玻璃板上以成為約80μm,於室溫下乾燥16小時後,於50℃乾燥1小時,且進一步於120℃乾燥1小時,而得到各種評估薄膜。所得之薄膜的膜厚,皆約為80μm。依循JIS Z 0208所記載之方法,對所得之薄膜測定透濕度。測定條件為40℃、相對濕度80%。透濕度,該數值小者,表示防濕性優異。防濕性能,透濕度為360g/m2/day以下者,表示性能優異。將所得之評估結果一同記載於下述第1表及第2表。
將纖維素三乙酸酯90質量份(乙醯化度61%、聚合度260)及改質劑10質量份,一邊攪拌一邊均一地溶解於由二氯甲烷900質量份與甲醇100質量份所構成之混合溶劑,調製出各種評估用及薄膜製作用摻雜液。接著將所得之摻雜液澆注於玻璃板上以成為約80μm,於室溫下乾燥16小時後,於50℃乾燥1小時,且進一步於120℃乾燥1小時,而得到各種評估薄膜。所得之薄膜的膜厚,皆約為80μm。於25℃、相對濕度15%的環境下使所得之薄膜乾燥48小時,以乾燥後的薄膜之厚度方向的相位差為「乾燥時相位差」,然後於40℃、相對濕度80%將相同的薄膜放置72小時後,以此時之薄膜之厚度方向的相位差為「高溫高濕時相位差」,並從下述式算出「相位差變
動值」,相位差變動值以絕對值表示。相位差變動值,數值愈小性能愈佳,為30以下時,表示性能優異。
|相位差變動值|=乾燥時相位差-高溫高濕時相位差
將纖維素三乙酸酯85質量份(乙醯化度61%、聚合度260)及改質劑15質量份,一邊攪拌一邊均一地溶解於由二氯甲烷900質量份與甲醇100質量份所構成之混合溶劑,調製出各種評估用及薄膜製作用摻雜液。接著將所得之摻雜液澆注於玻璃板上以成為約80μm,於室溫下乾燥16小時後,於50℃乾燥1小時,且進一步於120℃乾燥1小時,而得到各種評估薄膜。所得之薄膜的膜厚,皆約為80μm。於40℃、相對濕度80%的環境下將所得之薄膜靜置24小時後,以目視來確認,並以下述基準進行3階段評估。
優:未確認到薄膜的扭曲
良:確認到薄膜產生些微扭曲
不可:確認到薄膜產生大幅扭曲
尺寸穩定性能,優及良者,表示該性能優異。將所得之評估結果一同記載於下述第1表及第2表。
薄膜之厚度方向的相位差,係依循下述式,使用自動複折射率計RETS-100(大塚電子股份有限公司製),於25℃、相對濕度60%的環境下,於波長590nm來測定。
厚度方向的相位差={(nx+ny)/2-nz}×d
在此,式中,nx表示薄膜面內的折射率為最大之方向上的折射率,ny表示與nx呈直角之方向上之薄膜面內的折射率,nz表示薄膜之厚度方向的折射率,d表示薄膜的厚度(nm)。將所得之評估結果一同記載於下述第1表及第2表。
比較化合物1:磷酸三苯酯
比較化合物2:由琥珀酸(50)/對苯二甲酸(50)/乙二醇(100)所構成之縮合物的兩末端之未封止物(數量平均分子量:670)
比較化合物3:將比較化合物2的乙二醇取代為1,2-丙二醇之縮合物(數量平均分子量:1000)
比較化合物4:比較化合物2的縮合物(數量平均分子量:1400)
比較化合物5:由琥珀酸(50)/對苯二甲酸(50)/乙二醇(100)所構成之縮合物的兩末端之苯甲酸酯物(數量平均分子量:450)
比較化合物6:由琥珀酸(50)/對苯二甲酸(50)/1,2-丙二醇(100)所構成之縮合物的兩末端之苯甲酸酯物(數量平均分子量:450)
比較化合物7:比較化合物5的縮合物(數量平均分子量:1050)
比較化合物8:由琥珀酸(30)/對苯二甲酸(70)/1,2-丙二醇(100)所構成之縮合物的兩末端之苯甲酸酯物(數量平均分子量:1050)
比較化合物9:由琥珀酸(50)/對苯二甲酸(50)/乙二醇(100)所構成之縮合物的兩末端之正辛酸酯物(數量平均分子量:500)
比較化合物10:由琥珀酸(50)/對苯二甲酸(50)/乙二醇(100)所構成之縮合物的兩末端之乙酸酯物(數量平均分子量:1130)
比較化合物11:由己二酸(100)/乙二醇(100)所構成之縮合物的兩末端之苯甲酸酯物(數量平均分子量:1300)
比較化合物12:由對苯二甲酸(100)/1,2-丙二醇(100)所構成之縮合物的兩末端之苯甲酸酯物(數量平均分子量:480)
比較化合物13:由對苯二甲酸(100)/乙二醇(50)/1,2-丙二醇(50)所構成之縮合物的兩末端之對三級丁基苯甲酸酯物(數量平均分子量:500)
從第1表及第2表中,可得知本發明之改質劑皆可滿足防濕性(透濕度)、尺寸穩定性、光學特性(相位差變動值),相對於此,比較化合物,有時會有即使防濕性佳,光學特性亦差,或是尺寸穩定性佳,但防濕性與光學特性差之情形。因此,本發明係均衡性佳地達到防濕性、尺寸穩定性、光學特性之優異的樹脂用改質劑。
Claims (7)
- 如請求項1之樹脂用改質劑,其中以前述一般式(1)所示之化合物之RA、RB及RC,為碳原子數2~12的烴基,或是具有選自由氧原子、硫原子、氮原子所組成之群組之1個以上的原子之碳原子數2~12的烴基,前述烴基表示直鏈狀或分枝狀的伸烷基、直鏈狀或分枝狀的伸烯基、可具有直鏈狀或分枝狀的取代基之環伸烷基、可具有直鏈狀或分枝狀的取代基之伸芳基,前述取代基表示烷基或伸烷基。
- 如請求項1之樹脂用改質劑,其係用於熱塑性樹脂。
- 如請求項2之樹脂用改質劑,其係用於熱塑性樹脂。
- 如請求項3之樹脂用改質劑,其中前述熱塑性樹脂為纖維素系樹脂。
- 如請求項4之樹脂用改質劑,其中前述熱塑性樹脂為纖維素系樹脂。
- 一種樹脂組成物,其特徵為含有如請求項1之樹脂用改質劑。
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