TWI828776B - 樹脂組合物及光纖 - Google Patents

樹脂組合物及光纖 Download PDF

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TWI828776B
TWI828776B TW108136032A TW108136032A TWI828776B TW I828776 B TWI828776 B TW I828776B TW 108136032 A TW108136032 A TW 108136032A TW 108136032 A TW108136032 A TW 108136032A TW I828776 B TWI828776 B TW I828776B
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meth
acrylate
resin composition
resin layer
resin
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TW108136032A
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TW202033581A (zh
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浜窪勝史
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日商住友電氣工業股份有限公司
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Abstract

樹脂組合物包含基底樹脂與疏水性之無機氧化物粒子，上述基底樹脂含有(甲基)丙烯酸胺基甲酸酯低聚物、具有苯氧基之單體、光聚合引發劑及矽烷偶合劑，無機氧化物粒子之含量係以樹脂組合物之總量為基準而言為1質量%以上45質量%以下。

Description

樹脂組合物及光纖
本發明係關於一種樹脂組合物及光纖。
本申請要求基於2018年10月4日提出申請之日本專利申請第2018-189221號之優先權，上述日本專利申請中所記載之所有記載內容引用於本申請中。
通常情況下，光纖具有用於保護作為光傳輸體之玻璃纖維之被覆樹脂層。光纖為了減小由於對光纖賦予側壓時所產生之微小彎曲所引起之傳輸損耗之增加，要求側壓特性優異。
被覆樹脂層例如具備第1樹脂層及第2樹脂層。對於第1樹脂層，要求楊氏模數低且柔軟性優異(例如參照專利文獻1)。
[先前技術文獻] [專利文獻]
[專利文獻1]日本專利特開2013-197163號公報
本發明之一態樣之樹脂組合物包含基底樹脂與疏水性之無機氧化物粒子，上述基底樹脂含有(甲基)丙烯酸胺基甲酸酯低聚物、具有苯氧基之單體、光聚合起始劑及矽烷偶合劑，無機氧化物粒子之含量係以樹脂組合物之總量為基準而言為1質量%以上45質量%以下。
10:光纖
11:芯
12:包層
13:玻璃纖維
14:第1樹脂層
15:第2樹脂層
16:被覆樹脂層
D1:直徑
D2:外徑
圖1係表示本實施方式之光纖之一例的概略剖視圖。
[發明所欲解決之課題]
自提高光纖之側壓特性之觀點考慮，較佳為降低第1樹脂層之楊氏模數，但隨著第1樹脂層之楊氏模數變低，第1樹脂層之強度降低，變得容易於光纖中產生孔隙。
本發明之目的在於提供能夠形成孔隙之產生得到抑制，且使光纖之側壓特性提高的樹脂層之樹脂組合物，以及具備由該樹脂組合物所形成之第1樹脂層的光纖。
[發明之效果]
根據本發明，可提供能夠形成孔隙之產生得到抑制，且使光纖之側壓特性提高的樹脂層之光纖被覆用樹脂組合物，以及具備由該樹脂組合物所形成之第1樹脂層的光纖。
[本發明之實施方式之說明]
首先，列舉本發明之實施方式之內容而加以說明。本發明之一態樣之樹脂組合物包含基底樹脂與疏水性之無機氧化物粒子，上述基底樹脂含有(甲基)丙烯酸胺基甲酸酯低聚物、具有苯氧基之單體、光聚合起始劑及矽烷偶合劑，無機氧化物粒子之含量係以樹脂組合物之總量為基準而言為1質量%以上45質量%以下。
藉由於特定之範圍內與具有苯氧基之單體一同使用無機氧 化物粒子，能夠形成孔隙之產生得到抑制，且可使光纖之側壓特性提高的樹脂層。
自進而提高光纖之側壓特性考慮，具有苯氧基之單體之含量亦可係以基底樹脂之總量為基準而言為0.5質量%以上60質量%以下。
自於樹脂組合物中之分散性優異，容易形成強韌之樹脂層考慮，上述無機氧化物粒子可為選自由二氧化矽、二氧化鋯、氧化鋁、氧化鎂、氧化鈦、氧化錫及氧化鋅所組成之群中之至少1種。自使樹脂層之楊氏模數降低之觀點考慮，無機氧化物粒子之平均一次粒徑可為650nm以下。
本發明之一態樣之光纖的第1被覆材料包含上述樹脂組合物。藉由將本實施方式之樹脂組合物用於第1樹脂層，能夠製作抑制孔隙之產生，且側壓特性優異之光纖。
本發明之一態樣之光纖包括：玻璃纖維，其包含芯及包層；第1樹脂層，其與玻璃纖維相接並被覆該玻璃纖維；以及第2樹脂層，其被覆第1樹脂層，且第1樹脂層由上述樹脂組合物之硬化物構成。藉由將本實施方式之樹脂組合物應用於第1樹脂層，能夠提高光纖之側壓特性。
自進一步提高光纖之側壓特性之觀點考慮，上述樹脂組合物之硬化物之楊氏模數可於23℃±2℃下為4MPa以下。
[本發明之實施方式之詳細內容]
視需要參照圖式對本發明之實施方式之樹脂組合物及光纖之具體例加以說明。再者，本發明並不限於該等例示，其由發明申請專利範圍表示，包括與申請專利範圍均等之意思以及範圍內之所有變更。於以下之說 明中，於圖式說明中對同一元件標註同一符號，且省略重複之說明。
<樹脂組合物>
本實施方式之樹脂組合物包含基底樹脂及疏水性之無機氧化物粒子，上述基底樹脂含有(甲基)丙烯酸胺基甲酸酯低聚物、具有苯氧基之單體、光聚合起始劑及矽烷偶合劑。
此處，(甲基)丙烯酸酯係指丙烯酸酯或與其對應之甲基丙烯酸酯。關於(甲基)丙烯酸亦同樣如此。
(基底樹脂)
本實施方式之基底樹脂含有(甲基)丙烯酸胺基甲酸酯低聚物、具有苯氧基之單體、光聚合起始劑及矽烷偶合劑。藉由使用具有苯氧基之單體，能夠形成可抑制孔隙之產生，且使光纖之側壓特性提高的樹脂層。
作為具有苯氧基之單體，可以使用具有苯氧基之(甲基)丙烯酸酯化合物。作為具有苯氧基之(甲基)丙烯酸酯化合物，例如可列舉：苯酚EO改性(甲基)丙烯酸酯、壬基苯酚EO改性(甲基)丙烯酸酯、苯酚PO改性(甲基)丙烯酸酯、壬基苯酚PO改性(甲基)丙烯酸酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸2-羥基-3-苯氧基丙酯及(甲基)丙烯酸3-苯氧基苄酯。此處，所謂EO改性係指具有(C2H4O)n所表示之環氧乙烷基，所謂PO改性係指具有(C3H6O)n所表示之環氧丙烷基。n為1以上之整數。
自調整硬化物之楊氏模數之觀點考慮，具有苯氧基之單體可為選自由苯酚EO改性(甲基)丙烯酸酯、壬基苯酚EO改性(甲基)丙烯酸酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸2-羥基-3-苯氧基丙酯及(甲 基)丙烯酸3-苯氧基苄酯所組成之群中之至少1種。具有苯氧基之單體可混合使用2種以上。
具有苯氧基之單體之含量係以基底樹脂之總量為基準而言較佳為0.5質量%以上60質量%以下，更較佳為1質量%以上55質量%以下，進而更佳為2質量%以上50質量%以下。藉由使樹脂組合物於此種範圍內含有具有苯氧基之單體，可形成具有適當之楊氏模數的樹脂層而作為光纖之第1被覆材料。
基底樹脂亦可進而含有不具有苯氧基之單體。不具有苯氧基之單體可為具有1個聚合性基之單官能單體或具有2個以上聚合性基之多官能單體。不具有苯氧基之單體可混合使用2種以上。
作為不具有苯氧基之單官能單體，例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸正戊酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸月桂酯、4-第三丁基環己醇(甲基)丙烯酸酯、(甲基)丙烯酸四氫呋喃甲酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸雙環戊烯酯、(甲基)丙烯酸雙環戊烯氧基乙酯、(甲基)丙烯酸雙環戊酯、壬基苯酚聚乙二醇(甲基)丙烯酸酯、(甲基)丙烯酸異
Figure 108136032-A0305-02-0006-4
酯等(甲基)丙烯酸酯系單體；(甲基)丙烯酸、(甲基)丙烯酸二聚物、(甲基)丙烯酸羧基乙酯、(甲基)丙烯酸羧基戊酯、ω-羧基-聚己內酯(甲基)丙烯酸酯等含有羧基之單體；N-丙烯醯
Figure 108136032-A0305-02-0006-5
啉、N-乙烯基吡咯啶酮、N-乙烯基己內醯胺、N-丙烯醯基哌啶、N-甲基丙烯醯基哌啶、 N-丙烯醯基吡咯啶、(甲基)丙烯酸3-(3-吡啶)丙酯、環狀三羥甲基丙烷縮甲醛丙烯酸酯等含有雜環之(甲基)丙烯酸酯；馬來醯亞胺、N-環己基馬來醯亞胺、N-苯基馬來醯亞胺等馬來醯亞胺系單體；(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N,N-二乙基(甲基)丙烯醯胺、N-己基(甲基)丙烯醯胺、N-甲基(甲基)丙烯醯胺、N-丁基(甲基)丙烯醯胺、N-丁基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-羥甲基丙烷(甲基)丙烯醯胺等N-取代醯胺系單體；(甲基)丙烯酸胺基乙酯、(甲基)丙烯酸胺基丙酯、(甲基)丙烯酸N,N-二甲基胺基乙酯、(甲基)丙烯酸第三丁基胺基乙酯等(甲基)丙烯酸胺基烷基酯系單體；N-(甲基)丙烯醯氧基亞甲基琥珀醯亞胺、N-(甲基)丙烯醯基-6-氧基六亞甲基琥珀醯亞胺、N-(甲基)丙烯醯基-8-氧基八亞甲基琥珀醯亞胺等琥珀醯亞胺系單體。
作為不具有苯氧基之多官能單體，例如可列舉：乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、雙酚A之環氧烷加成物之二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、羥基新戊酸新戊二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、1,12-十二烷二醇二(甲基)丙烯酸酯、1,14-十四烷二醇二(甲基)丙烯酸酯、1,16-十六烷二醇二(甲基)丙烯酸酯、1,20-二十烷二醇二(甲基)丙烯酸酯、異戊二醇二(甲基)丙烯酸酯、3-乙基-1,8-辛二醇二(甲基)丙烯酸酯、雙酚A之EO加成物之二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、三羥甲基辛烷三(甲基)丙烯酸酯、三羥甲基丙烷聚乙氧基三(甲基)丙烯酸酯、三羥甲基丙烷聚丙氧基三(甲基)丙烯酸酯、三羥甲基丙烷聚乙氧基聚丙氧基三(甲基)丙 烯酸酯、異氰尿酸三[(甲基)丙烯醯氧基乙基]酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇聚乙氧基四(甲基)丙烯酸酯、季戊四醇聚丙氧基四(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二-三羥甲基丙烷四(甲基)丙烯酸酯、二季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯及己內酯改性異氰尿酸三[(甲基)丙烯醯氧基乙基]酯。
作為多官能單體，自降低樹脂組合物之黏度，形成具有所期望之楊氏模數之塗膜之觀點考慮，可使用三丙二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯。其中，作為多官能單體較佳為1,6-己二醇二(甲基)丙烯酸酯。
作為(甲基)丙烯酸胺基甲酸酯低聚物，可使用使多元醇化合物、聚異氰酸酯化合物及含有羥基之(甲基)丙烯酸酯化合物反應而獲得之低聚物。
作為多元醇化合物，例如可列舉聚四亞甲基二醇、聚丙二醇及雙酚A-環氧乙烷加成二醇。多元醇化合物之數量平均分子量較佳為1000以上8000以下，更佳為1200以上6500以下，進而更佳為1500以上6000以下。作為聚異氰酸酯化合物，例如可列舉：2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯、異佛爾酮二異氰酸酯及二環己基甲烷4,4'-二異氰酸酯。作為含有羥基之(甲基)丙烯酸酯化合物，例如可列舉：(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丁酯、1,6-己二醇單(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、(甲基)丙烯酸2-羥基丙酯及三丙二醇單(甲基)丙烯酸酯。
作為合成(甲基)丙烯酸胺基甲酸酯低聚物時之觸媒，通常 使用有機錫化合物。作為有機錫化合物，例如可列舉：二月桂酸二丁基錫、二乙酸二丁基錫、馬來酸二丁基錫、雙(巰基乙酸2-乙基己酯)二丁基錫、雙(巰基乙酸異辛酯)二丁基錫及二丁基氧化錫。自易取得性或觸媒性能之方面考慮，較佳為使用二月桂酸二丁基錫或二乙酸二丁基錫作為觸媒。
於合成(甲基)丙烯酸胺基甲酸酯低聚物時，可使用碳數為5以下之低級醇。作為低級醇，例如可列舉：甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇、2-甲基-2-丙醇、1-戊醇、2-戊醇、3-戊醇、2-甲基-1-丁醇、3-甲基-1-丁醇、2-甲基-2-丁醇、3-甲基-2-丁醇及2,2-二甲基-1-丙醇。
本實施方式之基底樹脂可進而含有環氧(甲基)丙烯酸酯低聚物作為低聚物。作為環氧(甲基)丙烯酸酯低聚物，可使用使具有(甲基)丙烯醯基的化合物與具有2個以上縮水甘油基之環氧樹脂反應而獲得之低聚物。
作為光聚合起始劑，可自公知之自由基光聚合起始劑中適宜選擇而使用。作為光聚合起始劑，例如可列舉：1-羥基環己基苯基酮、2,2-二甲氧基-2-苯基苯乙酮、1-(4-異丙基苯基)-2-羥基-2-甲基丙烷-1-酮、雙(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基戊基氧化膦、2-甲基-1-[4-(甲硫基)苯基]-2-
Figure 108136032-A0305-02-0009-6
啉酮-丙烷-1-酮(Omnirad 907、IGM Resins公司製造)、2,4,6-三甲基苯甲醯基二苯基氧化膦(Omnirad TPO、IGM Resins公司製造)及雙(2,4,6-三甲基苯甲醯基)苯基氧化膦(Omnirad 819、IGM Resins公司製造)。
作為矽烷偶合劑，只要不妨礙樹脂組合物的硬化，則並無 特別限定。作為矽烷偶合劑，例如可列舉：矽酸四甲酯、矽酸四乙酯、巰基丙基三甲氧基矽烷、乙烯基三氯矽烷、乙烯基三乙氧基矽烷、乙烯基三(β-甲氧基-乙氧基)矽烷、β-(3,4-環氧環己基)-乙基三甲氧基矽烷、二甲氧基二甲基矽烷、二乙氧基二甲基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷、γ-縮水甘油氧基丙基三甲氧基矽烷、γ-縮水甘油氧基丙基甲基二乙氧基矽烷、γ-甲基丙烯醯氧基丙基三甲氧基矽烷、N-(β-胺基乙基)-γ-胺基丙基三甲氧基矽烷、N-(β-胺基乙基)-γ-胺基丙基三甲基二甲氧基矽烷、N-苯基-γ-胺基丙基三甲氧基矽烷、γ-氯丙基三甲氧基矽烷、γ-巰基丙基三甲氧基矽烷、γ-胺基丙基三甲氧基矽烷、雙-[3-(三乙氧基矽烷基)丙基]四硫化物、雙-[3-(三乙氧基矽烷基)丙基]二硫化物、γ-三甲氧基矽烷基丙基二甲基硫代胺基甲醯基四硫化物及γ-三甲氧基矽烷基丙基苯并噻唑基四硫化物。
樹脂組合物亦可進而含有光酸產生劑、調平劑、消泡劑、抗氧化劑等。
作為光酸發生劑，可使用具有A+B-之結構之鎓鹽。作為光酸產生劑，例如可列舉：UVACURE1590(Daicel-Cytec製造)、CPI-100P、110P(San-Apro製造)等鋶鹽，Omnicat 250(IGM Resins公司製造)、WPI-113(富士膠片和光純藥製造)、Rp-2074(Rhodia Japan製造)等錪鹽。
(無機氧化物粒子)
本實施方式之無機氧化物粒子之表面進行了疏水處理。本實施方式之疏水處理係指於無機氧化物粒子之表面導入疏水性基。導入有疏水性基 之無機氧化物粒子於樹脂組合物中之分散性優異。疏水性基可為(甲基)丙烯醯基、乙烯基等反應性基，或烴基(例如烷基)、芳基(例如苯基)等非反應性基。於無機氧化物粒子具有反應性基之情形時，變得容易形成楊氏模數高之樹脂層。
本實施方式之無機氧化物粒子分散於分散介質中。藉由使用分散於分散介質中之無機氧化物粒子，可於樹脂組合物中均勻地分散無機氧化物粒子，且可提高樹脂組合物之保存穩定性。作為分散介質，只要不阻礙樹脂組合物之硬化，就沒有特別限定。分散介質可為反應性者，亦可為非反應性者。
作為反應性之分散介質，可使用(甲基)丙烯醯基化合物、環氧化合物等單體。作為(甲基)丙烯醯基化合物，例如可列舉：1,6-己二醇二(甲基)丙烯酸酯、EO改性雙酚A二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、PO改性雙酚A二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯及聚四亞甲基二醇二(甲基)丙烯酸酯。作為(甲基)丙烯醯基化合物，亦可使用上述單體中所例示之化合物。
作為非反應性之分散介質，可使用甲基乙基酮(MEK)等酮系溶劑，甲醇(MeOH)、丙二醇單甲醚(PGME)等醇系溶劑，或丙二醇單甲醚乙酸酯(PGMEA)等酯系溶劑。於非反應性之分散介質之情形時，可將基底樹脂與分散於分散介質中之無機氧化物粒子加以混合，然後除去分散介質之一部分而製備樹脂組合物。藉由光學顯微鏡(倍率約為100倍)觀察含有無機氧化物粒子之分散介質，於未觀察到粒子之情形時，可以說無機氧化物粒子以一次粒子之形式進行分散。
分散於分散介質中之無機氧化物粒子於樹脂組合物之硬化 後亦以分散於樹脂層中之狀態存在。於使用反應性之分散介質之情形時，無機氧化物粒子與分散介質一同混合於樹脂組合物中，於維持分散狀態之狀態下摻入至樹脂層中。於使用非反應性之分散介質之情形時，分散介質之至少一部分從樹脂組合物揮發而消失，但無機氧化物粒子維持分散狀態而殘留於樹脂組合物中，且於硬化後之樹脂層中亦以分散狀態存在。於藉由電子顯微鏡觀察存在於樹脂層中之無機氧化物粒子之情形時，於以一次粒子分散之狀態下被觀察到。
自於樹脂組合物中之分散性優異、容易形成強韌之樹脂層考慮，上述無機氧化物粒子較佳為選自由二氧化矽(氧化矽)、二氧化鋯(氧化鋯)、氧化鋁(alumina)、氧化鎂(magnesia)、氧化鈦(titania)、氧化錫及氧化鋅所組成之群中之至少1種。自廉價性優異、容易進行表面處理、具有紫外線透過性、容易對樹脂層賦予適度之硬度等觀點考慮，作為本實施方式之無機氧化物粒子，更佳為使用疏水性之氧化矽粒子。
自降低第1樹脂層之楊氏模數之觀點考慮，無機氧化物粒子之平均一次粒徑可為650nm以下，較佳為600nm以下，更佳為500nm以下，進而較佳為400nm以下。自賦予第1樹脂層之強度之觀點考慮，無機氧化物粒子之平均一次粒徑較佳為5nm以上，更佳為10nm以上。平均一次粒徑例如可藉由電子顯微鏡照片之圖像解析、光散射法、BET法等而測定。分散有無機氧化物粒子之一次粒子的分散介質於一次粒子之粒徑較小時，於目視下看起來透明。於一次粒子之粒徑較大(40nm以上)之情形時，分散有一次粒子之分散介質看起來白濁，但未觀察到沈澱物。
無機氧化物粒子之含量係以樹脂組合物之總量(基底樹脂及無機氧化物粒子之總量)為基準而言為1質量%以上45質量%以下，較佳為 2質量%以上40質量%以下，更佳為3質量%以上35質量%以下。若無機氧化物粒子之含量為1質量%以上，則變得容易形成強韌之樹脂層。若無機氧化物粒子之含量為45質量%以下，則變得容易形成楊氏模數低之樹脂層。再者，可認為樹脂組合物之總量與樹脂組合物之硬化物之總量相同。無機氧化物粒子的含量係以第1樹脂層之總量(構成第1樹脂層之樹脂組合物之硬化物之總量)為基準而言為1質量%以上45質量%以下，較佳為2質量%以上40質量%以下，更佳為3質量%以上35質量%以下。
自抑制於光纖中產生孔隙之方面考慮，上述樹脂組合物之硬化物之楊氏模數較佳為於23℃±2℃下為4MPa以下，更佳為0.05MPa以上4.0MPa以下，進而較佳為0.1MPa以上3.5MPa以下，特佳為0.3MPa以上3.0MPa以下。
本實施方式之樹脂組合物可較佳地用作光纖之第1被覆材料。藉由將本實施方式之樹脂組合物用於第1樹脂層中，可以製作楊氏模數得到降低且抑制孔隙之產生，側壓特性優異之光纖。
<光纖>
圖1係表示本實施方式之光纖之一例的概略剖視圖。光纖10包含：玻璃纖維13，其包含芯11及包層12；被覆樹脂層16，其包含設於玻璃纖維13之外周的第1樹脂層14及第2樹脂層15。
包層12包圍芯11。芯11及包層12主要包含石英玻璃等玻璃，例如芯11可使用添加有鍺之石英，包層12可使用純石英、或添加有氟之石英。
於圖1中，例如玻璃纖維13之外徑(D2)為125μm左右，構 成玻璃纖維13之芯11之直徑(D1)為7~15μm左右。
被覆樹脂層16之厚度通常為60~70μm左右。第1樹脂層14及第2樹脂層15之各層之厚度可為10~50μm左右，例如可以是第1樹脂層14之厚度為35μm、第2樹脂層15之厚度為25μm。光纖10之外徑可為245~265μm左右。
又，被覆樹脂層16之厚度可為27~48μm左右。第1樹脂層14及第2樹脂層15之各層之厚度可為10~38μm左右，例如可以是第1樹脂層14之厚度為25μm，第2樹脂層15之厚度為10μm。光纖10之外徑可為179~221μm左右。
進而，亦可為玻璃纖維13之外徑(D2)為100μm左右，被覆樹脂層16之厚度為22~37μm左右。第1樹脂層14及第2樹脂層15之各層之厚度可為5~32μm左右，例如可以是第1樹脂層14之厚度為25μm，第2樹脂層15之厚度為10μm。光纖10之外徑可為144~174μm左右。
第2樹脂層之楊氏模數較佳為於23℃下為1300MPa以上，更較佳為1300MPa以上2600MPa以下，進一步較佳為1300MPa以上2500MPa以下。若第2樹脂層之楊氏模數為1300MPa以上，則容易提高側壓特性，若為2600MPa以下，則可對第2樹脂層賦予適度之韌性，因此變得難以於第2樹脂層產生裂紋等。
第2層例如可藉由使含有(甲基)丙烯酸胺基甲酸酯低聚物、單體及光聚合起始劑的樹脂組合物硬化而形成。第2樹脂層用之樹脂組合物可使用先前公知之技術。作為(甲基)丙烯酸胺基甲酸酯低聚物、單體及光聚合起始劑，可自上述基底樹脂中所例示之化合物中適當選擇。又，第2樹脂層用之樹脂組合物亦可含有疏水性之無機氧化物粒子。但是，形成 第2樹脂層之樹脂組合物具有與形成第1樹脂層之樹脂組合物不同之組成。自提高第2樹脂層之楊氏模數之觀點考慮，合成(甲基)丙烯酸胺基甲酸酯低聚物時所使用之多元醇化合物之數量均分子量可為400以上1000以下。
[實施例]
以下，示出使用本發明之實施例及比較例的評價試驗之結果，對本發明加以更詳細之說明。再者，本發明並不限定於該等實施例。
[樹脂組合物之製作] (低聚物)
作為低聚物，準備分子量為4000之藉由使聚丙二醇、異佛爾酮二異氰酸酯、丙烯酸羥基乙酯及甲醇反應而獲得之丙烯酸胺基甲酸酯低聚物。
(具有苯氧基之單體)
作為具有苯氧基之單體，準備壬基苯酚EO改性丙烯酸酯(東亞合成股份有限公司之商品名「ARONIX M-113」、n≒4)、壬基苯酚EO改性丙烯酸酯(東亞合成股份有限公司之商品名「ARONIX M-111、n≒1)、苯酚EO改性丙烯酸酯(東亞合成股份有限公司之商品名「ARONIX M-101A、n≒2)、苯酚EO改性丙烯酸酯(東亞合成股份有限公司之商品名「ARONIX M-102、n≒4)、丙烯酸苯氧基乙酯(共榮化學股份有限公司之商品名「Light acrylate PO-A」)、及丙烯酸3-苯氧基苄酯(共榮化學股份有限公司之商品名「Light acrylate POB-A」)、丙烯酸2-羥基-3-苯氧基丙酯(共榮化學股份有限公司之商品名「Epoxy Ester M-600A」)。
(不具有苯氧基之單體)
作為不具有苯氧基之單體，準備N-乙烯基己內醯胺及1,6-己二醇二丙烯酸酯。
(光聚合起始劑)
作為光聚合起始劑，準備2,4,6-三甲基苯甲醯基二苯基氧化膦。
(矽烷偶合劑)
作為矽烷偶合劑，準備3-巰基丙基三甲氧基矽烷。
(無機氧化物粒子)
作為無機氧化物粒子，準備平均粒徑為10nm以上15nm以下之疏水性氧化矽粒子、平均粒徑為70nm以上100nm以下之疏水性氧化矽粒子、平均粒徑為250nm以上350nm以下之疏水性氧化矽粒子、及平均粒徑為450nm以上640nm以下之疏水性氧化矽粒子。該等氧化矽粒子具有甲基丙烯醯基，分散於甲基乙基酮(MEK)中。
(樹脂組合物)
首先，將上述低聚物、單體、光聚合起始劑及矽烷偶合劑加以混合而製備基底樹脂。其次，將基底樹脂與氧化矽粒子加以混合後，減壓除去作為分散介質之MEK之大部分，分別製作實施例及比較例之樹脂組合物。再者，樹脂組合物中所殘存之MEK之含量為5質量%以下。
於表1、表2及表3中，單體、低聚物及矽烷偶合劑之各數 值係以單體、低聚物、矽烷偶合劑及氧化矽粒子之總量為基準的含量(質量%)，氧化矽粒子之數值係以樹脂組合物之總量為基準的含量。
使用實施例及比較例中所獲得之樹脂組合物而進行以下評價。
(楊氏模數)
使用旋轉塗佈機，將樹脂組合物塗佈於聚對苯二甲酸乙二酯(PET)膜上之後，使用無電極UV燈系統(D BULB)(賀利氏公司製造)，於1000±100mJ/cm2之條件下使其硬化，於PET膜上形成厚度為200±20μm之樹脂層。將樹脂層自PET膜剝下而獲得樹脂膜。
將樹脂膜沖裁為JIS K 7127之類型5之啞鈴形狀，於23±2℃、50±10%RH之條件下，使用拉力試驗機以1mm/分鐘之拉伸速度、標線間25mm之條件下進行拉伸，獲得應力-應變曲線。藉由2.5%割線求得楊氏模數。
[光纖之製作]
將分子量為600之聚丙二醇、2,4-甲苯二異氰酸酯及丙烯酸2-羥基乙酯之反應物的丙烯酸胺基甲酸酯低聚物40質量份、異
Figure 108136032-A0305-02-0017-7
基丙烯酸酯35質量份、雙酚A二縮水甘油醚-丙烯酸加成物24質量份、2,4,6-三甲基苯甲醯基二苯基氧化膦0.5質量份、1-羥基環己基苯基酮0.5質量份加以混合而製作第2樹脂層用之樹脂組合物A1。
於由芯及包層所構成之直徑為125μm之玻璃纖維之外周，使用實施例或比較例中所製作之樹脂組合物而形成厚度為35μm之第1樹脂 層，進而於其外周使用樹脂組合物A1而形成第2樹脂層，製作光纖。線速度為1500m/分鐘。
(孔隙之觀察)
將10m之光纖於85℃、濕度85%之條件下保管120日之後，於-40℃下放置16小時，藉由顯微鏡觀察直徑10μm以上之孔隙之有無。將每1m光纖之孔隙數未達1個之情形評價為「A」，將孔隙數為1~2個之情形評價為「B」，將孔隙數超過2個之情形評價為「C」。
(側壓特性)
利用OTDR(Optical Time Domain Reflectometer，光時域反射計)法測定於藉由砂紙覆蓋表面之直徑為280mm之繞線筒上，將光纖捲繞為單層狀時之波長為1550nm之光之傳輸損耗。又，利用OTDR法測定於沒有砂紙之直徑為280mm之繞線筒上，將光纖10捲繞為單層狀時之波長為1550nm之光之傳輸損耗。求出所測定之傳輸損耗之差，將傳輸損耗差為0.6dB/km以下之情形判斷為側壓特性「OK」，將傳輸損耗差超過0.6dB/km之情形判斷為側壓特性「NG」。
Figure 108136032-A0305-02-0018-1
Figure 108136032-A0305-02-0019-2
Figure 108136032-A0305-02-0019-3
可確認：實施例之樹脂組合物可以製作具有第1樹脂層所要求之楊氏模數，並且孔隙之產生得到抑制，且使側壓特性提高之光纖。
10:光纖
11:芯
12:包層
13:玻璃纖維
14:第1樹脂層
15:第2樹脂層
16:被覆樹脂層
D1:直徑
D2:外徑

Claims (8)

  1. 一種光纖被覆用之樹脂組合物，其包含基底樹脂與疏水性之無機氧化物粒子，上述基底樹脂含有(甲基)丙烯酸胺基甲酸酯低聚物、具有苯氧基之單體、光聚合起始劑及矽烷偶合劑，上述基底樹脂進而含有多官能(甲基)丙烯酸酯作為不具有苯氧基之單體，上述無機氧化物粒子之含量係以上述樹脂組合物之總量為基準而言為1質量%以上45質量%以下。
  2. 如請求項1之樹脂組合物，其中上述具有苯氧基之單體之含量係以上述基底樹脂之總量為基準而言為0.5質量%以上60質量%以下。
  3. 如請求項1或2之樹脂組合物，其中上述無機氧化物粒子係選自由二氧化矽、二氧化鋯、氧化鋁、氧化鎂、氧化鈦、氧化錫及氧化鋅所組成之群中之至少1種。
  4. 如請求項1或2之樹脂組合物，其中上述無機氧化物粒子之平均一次粒徑為650nm以下。
  5. 如請求項1或2之樹脂組合物，其中上述具有苯氧基之單體係選自由苯酚EO改性(甲基)丙烯酸酯、壬基苯酚EO改性(甲基)丙烯酸酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸2-羥基-3-苯氧基丙酯、及(甲基)丙烯酸3- 苯氧基苄酯所組成之群中之至少1種。
  6. 一種光纖之第1被覆材料，其包含如請求項1至5中任一項之樹脂組合物。
  7. 一種光纖，其包括：玻璃纖維，其包含芯及包層；第1樹脂層，其與上述玻璃纖維相接並被覆該玻璃纖維；第2樹脂層，其被覆上述第1樹脂層，且上述第1樹脂層由如請求項1至5中任一項之樹脂組合物之硬化物構成。
  8. 如請求項7之光纖，其中上述樹脂組合物之硬化物之楊氏模數於23℃±2℃下為4MPa以下。
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