TW201512245A - 表面改質劑及物品 - Google Patents
表面改質劑及物品 Download PDFInfo
- Publication number
- TW201512245A TW201512245A TW103119546A TW103119546A TW201512245A TW 201512245 A TW201512245 A TW 201512245A TW 103119546 A TW103119546 A TW 103119546A TW 103119546 A TW103119546 A TW 103119546A TW 201512245 A TW201512245 A TW 201512245A
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- Taiwan
- Prior art keywords
- group
- treated
- surface modifier
- modifying agent
- integer
- Prior art date
Links
- 239000003607 modifier Substances 0.000 title claims abstract description 29
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- 239000004811 fluoropolymer Substances 0.000 claims abstract description 19
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- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical class CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
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- 239000012280 lithium aluminium hydride Substances 0.000 description 1
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000005246 nonafluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
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- LGUZHRODIJCVOC-UHFFFAOYSA-N perfluoroheptane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LGUZHRODIJCVOC-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 230000001737 promoting effect Effects 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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Abstract
本發明之課題在於提供一種可得到具有撥水撥油性、高滑水性,且耐UV性、耐熱性、耐藥性(耐鹼性)優異之塗膜之表面改質劑,以及經該表面改質劑處理之物品。
本發明之解決手段為一種表面改質劑,其係含有:選自以下列一般式(1)所示之含有有機矽之氟聚合物化合物、其部分水解物以及此等之部分水解縮合物的1種或2種以上。
□(式中,Rf表示碳數1~10之直鏈狀或分枝鏈狀的全氟烷基;a、b、c、d、e、f分別獨立地表示0或1以上的整數,a+b+c+d+e為1以上;a、b、c、d、e的括弧內之
各重複單位的存在順序,於式中並未限定;g為0或1,h、k為2~6的整數,m為1~3的整數;X表示氟原子或三氟甲基,R1、R2、R3分別獨立地表示碳數1~10的1價烴基,Z表示水解性基)
Description
本發明係關於在各種基材的表面上形成賦予防污、低摩擦(滑動性)等功能之層時所使用之表面改質劑,以及經該表面改質劑處理之物品。
以往,於後述種種專利文獻中,係提出具有水解性矽烷基之氟聚合物、以及以此等聚合物對各種基材的表面進行塗膜處理以賦予撥水性或防污性之方法。此等施以塗膜之製品,有時會在室外使用,因而要求耐紫外線(UV)性。此外,當使用玻璃為基材時,於製造步驟中,有時會接觸於鹼等之藥品或是經過熱處理步驟,從此等觀點來看,係要求耐藥性、耐熱性的提升。
日本特許第2705105號公報(專利文獻1),係在連結氟聚合物部位與水解性矽烷基之連結部位上含有碘原子。此時,於長期使用時,有時會產生碘脫離而著色之情形,由脫離所造成之結構變化,可能導致耐UV性、耐熱性劣化。
日本特表2008-534696號公報(專利文獻2)
中,係記載有在氟聚合物部位與水解性矽烷基之連結部位上具有以X所示之二價的有機基之內容。然而,並無X為含有Si元素之明確記載,於實施例中,僅有X為O(氧原子)之例示。當X為O時,由於形成醚鍵,所以分子的旋轉自由度增加,雖可期待滑動性的提升,但相反卻使耐UV性、耐熱性、耐藥性劣化。
日本特許第4672095號公報(專利文獻3)中,亦在連結氟聚合物與水解性矽烷基之連結基上包含醚鍵,所以耐UV性、耐熱性、耐藥性劣化。
日本特許第5074927號公報(專利文獻4)中,係在氟聚合物部位與水解性矽烷基之連結部位上中介存在有聚矽氧(矽氧烷)間隔材。一般而言,矽氧烷鍵的耐UV性和耐熱性優異,但相對於酸或鹼等之藥品之耐久性差。
日本特開2012-157856號公報(專利文獻5)亦與前述相同,在氟聚合物與水解性矽烷基之連結部位含有矽氧烷鍵。
日本特開2012-072272號公報(專利文獻6)中,係記載有在氟聚合物與水解性矽烷基之連結基上具有2價的有機基Q之內容,但關於含有Si之內容並無記載。此外,由於具有矽氧烷結構或是具有醚鍵之結構,所以耐UV性、耐熱性、耐藥性差。
日本特許第2860979號公報(專利文獻7)中,氟聚合物與水解性矽烷基之連結基為短鏈伸烷基,而
成為簡單結構,結構上雖然耐久性優異,但作為在玻璃基板表面的塗膜之鹼耐久性不足,而要求更進一步的提升。
〔專利文獻1〕日本特許第2705105號公報
〔專利文獻2〕日本特表2008-534696號公報
〔專利文獻3〕日本特許第4672095號公報
〔專利文獻4〕日本特許第5074927號公報
〔專利文獻5〕日本特開2012-157856號公報
〔專利文獻6〕日本特開2012-072272號公報
〔專利文獻7〕日本特許第2860979號公報
本發明係鑒於上述情形而創作出,該目的在於提供一種可得到具有撥水撥油性、高滑水性,且耐UV性、耐熱性、耐藥性(耐鹼性)優異之塗膜之表面改質劑,以及經該表面改質劑處理之物品。
本發明者們係為了達成上述目的,對耐UV性、耐熱性、耐藥性之更進一步的提升進行精心探討,結果發現到將矽伸烷基結構導入於以下列一般式(1)所示
之氟聚合物與水解性矽烷基之連結基之含有有機矽之氟聚合物化合物、其部分水解物或此等之部分水解縮合物,可有效於作為具有撥水撥油性、高滑水性,且耐UV性、耐熱性、耐藥性優異之表面改質劑,因而完成本發明。
因此,本發明係提供下列表面改質劑及物品。
〔1〕
一種表面改質劑,其係含有:以下列一般式(1)所示之含有有機矽之氟聚合物化合物、其部分水解物以及此等之部分水解縮合物的1種或2種以上,
(式中,Rf表示碳數1~10之直鏈狀或分枝鏈狀的全氟烷基;a、b、c、d、e、f分別獨立地表示0或1以上的整數,a+b+c+d+e為1以上;a、b、c、d、e的括弧內之各重複單位的存在順序,於式中並未限定;g為0或1,h、k為2~6的整數,m為1~3的整數;X表示氟原子或三氟甲基,R1、R2、R3分別獨立地表示碳數1~10的1價烴基,Z表示水解性基)。
〔2〕
如〔1〕之表面改質劑,其中於一般式(1)中,h為2,k為2。
〔3〕
如〔1〕之表面改質劑,其中於一般式(1)中,h為3,k為3。
〔4〕
如〔1〕~〔3〕中任一項之表面改質劑,其中以一般式(1)所示之含有有機矽之氟聚合物化合物的數量平均分子量為500~50,000。
〔5〕
一種物品,其係經如〔1〕~〔4〕中任一項之表面改質劑處理。
〔6〕
一種光學物品,其係經如〔1〕~〔4〕中任一項之表面改質劑處理。
〔7〕
一種觸控面板,其係經如〔1〕~〔4〕中任一項之表面改質劑處理。
〔8〕
一種抗反射薄膜,其係經如〔1〕~〔4〕中任一項之表面改質劑處理。
〔9〕
一種SiO2處理玻璃,其係經如〔1〕~〔4〕中任一項之表面改質劑處理。
〔10〕
一種強化玻璃,其係經如〔1〕~〔4〕中任一項之表面改質劑處理。
〔11〕
一種石英基板,其係經如〔1〕~〔4〕中任一項之表面改質劑處理。
本發明之表面改質劑,由於含有在氟聚合物與水解性矽烷基之連結部位上具有矽伸烷基結構之含有有機矽之氟聚合物化合物、其部分水解物或此等之部分水解縮合物,所以可形成具有撥水撥油性、高滑水性,且耐UV性、耐熱性、耐藥性優異之塗膜層。
本發明之表面改質劑,其係含有:以下列一般式(1)所示之含有有機矽之氟聚合物化合物(含氟有機矽烷化合物)、其部分水解物或此等之部分水解縮合物。
上述一般式(1)中,Rf為碳數1~10,較佳為1~6之直鏈狀或分枝鏈狀的全氟烷基,具體可列舉出三氟甲基、五氟乙基、七氟丙基、1-(三氟甲基)-1,2,2,2-四氟乙基、九氟丁基、1,1-二(三氟甲基)-2,2,2-三氟乙基、十一氟戊基、十三氟己基、十五氟庚基、十七氟辛基等,當中較佳為三氟甲基、五氟乙基、七氟丙基、九氟丁基、十一氟戊基、十三氟己基,特佳為三氟甲基、五氟乙基、七氟丙基。
此外,a、b、c、d、e、f分別獨立地表示0或1以上的整數,a+b+c+d+e為1以上。較佳者,a為0~100,b為0~150,c為0~150,d為1~200,e為1~200,f為0~5,a+b+c+d+e為1~300,特佳者,a為0~50,b為0~100,c為0~100,d為1~100,e為1~100,f為0~3,a+b+c+d+e為2~100。a、b、c、d、e的括弧內之各重複單位的存在順序,於式中並未限定。
再者,g為0或1,h、k為2~6的整數,m為1~3的整數,較佳者,h為2或3,k為2或3,m為2或3。
此外,X為氟原子或三氟甲基。
此外,R1、R2、R3為碳數1~10,較佳為1~8的1價烴基,R1、R2、R3的具體例,可列舉出甲基、乙基、正丙基、異丙基、正丁基、異丁基等之飽和烴基;苯基、苄基、1-苯基乙基等之芳香族烴基等,較佳為甲基。
Z為羥基或可水解之取代基。可水解之取代基,可例示出下列基,例如可列舉出甲氧基、乙氧基、丙氧基般之烷氧基,三氟甲氧基、三氟乙氧基、三氯乙氧基般之鹵化烷氧基;甲氧乙氧基般之烷氧基取代烷氧基;乙醯氧基、丙醯氧基、苯甲醯氧基般之醯氧基;異丙烯氧基、異丁烯氧基般之烯氧基;二甲基酮肟基、甲基乙基酮肟基、二乙基酮肟基、環己烷酮肟基般之亞胺氧基;甲基胺基、乙基胺基、二甲基胺基、二乙基胺基般之取代胺基;N-甲基乙醯胺基、N-乙基醯胺基般之醯胺基;二甲基胺氧基、二乙基胺氧基般之取代胺氧基;氯原子等之鹵素基等。Z的例子中,較佳為羥基、甲氧基、乙氧基、三氟乙氧基、乙醯氧基、異丙烯氧基、氯原子、二甲基酮肟基、甲基乙基酮肟基,特佳為羥基及甲氧基。Z可作為1種或2種以上的組合包含於本發明之含氟有機矽烷化合物。
本發明所使用之含氟有機矽烷化合物,較佳係使用:藉由凝膠滲透層析法所求得之聚苯乙烯換算的數量平均分子量較佳為500以上50,000以下,特佳為500以上30,000以下,更佳為1,000以上20,000以下的範圍
者。當數量平均分子量未達500時,有時無法充分地發揮作為全氟伸烷醚結構的特徵之撥水撥油性、防污性,超過50,000時,末端官能基的濃度過小,與基材之反應性或緊密性有時會降低。
本發明所提及之數量平均分子量,是指依據在下列條件所測定之凝膠滲透層析法(GPC:Gel Permeation Chromatography)所求得之聚苯乙烯換算的數量平均分子量(以下相同)。
〔測定條件〕
開展溶劑:氫氟氯碳(HCFC)-225
流量:1mL/min.
檢測器:蒸發光散射檢測器
管柱:Tosoh公司製TSKgel Multipore HXL-M
7.8mm ×30cm使用2根
管柱溫度:35℃
試樣注入量:100μL(濃度0.3質量%的HCFC-225溶液)
本發明所使用之含氟有機矽烷化合物,較佳係使用:由19F-NMR所求取之氟原子量為20質量%以上且未達70質量%,特佳為40質量%以上且未達70質量%的範圍者。當氟原子量未達20質量%時,有時無法得到目的之撥水撥油性、防污性等特性,70質量%以上時,有時無法得到目的之緊密性或耐久性。
以上述一般式(1)所示之含氟有機矽烷化合
物,例如可在自由基起始劑的存在下,藉由一般所知的方法使以下列一般式(I)所示之於末端具有碘之含氟化合物、與以下列一般式(II)所示之矽烷化合物反應後,使用還原劑等,藉由一般所知的方法將化合物中的碘還原而製得。
(式中,Rf、R1~R3、X、a、b、c、d、e、f、g、k、m以及a+b+c+d+e與上述相同;n為0~4的整數,較佳為0或1)
在此,所謂以式(I)所示之於末端具有碘之含氟化合物,可列舉出以下列所示者。
(式中,a、b、c、d、e與上述相同)
此外,以式(II)所示之矽烷化合物,可列舉出以下列所示者。
上述以一般式(I)所示之於末端具有碘之含氟化合物與以一般式(II)所示之矽烷化合物之反應比率,由以式(I)所示之於末端具有碘之含氟化合物的末端碘基、與以式(II)所示之矽烷化合物之烯基之莫耳比(烯基/碘基)計,為0.5~20.0,特佳為1.0~10.0。
上述反應條件,例如可在乾燥氮氣氛圍下,相對於碘基而言添加0.001~1莫耳當量的自由基起始劑,並於內溫50~180℃加熱30分鐘~4小時。自由基起始劑,可列舉出過氧化二苯甲醯、過氧化二異丙苯、過氧化二
(三級丁基)、三級丁基過氧基乙酸酯、三級丁基過氧基苄酸酯、2,5-二甲基-2,5-二(三級丁基)過氧基己烷、三級丁基過氧基異丙基單碳酸酯、2,2'-偶氮雙異丁腈等之偶氮系起始劑等。
所得之化合物中的碘,可藉由使用氫化硼鈉、氫化鋰鋁等之氫化物,或是鐵、鋅、鎳、鋁、鎂等之金屬來還原。還原劑的量,以還原當量來考慮時,相對於碘的量而言較佳為1當量以上,尤佳為1.5當量以上。還原反應的溫度、時間,可因應還原劑的種類及方法,以最適條件來進行,一般可在室溫(23℃)~100℃、於1~24小時的範圍內進行。
如此得到之以式(1)所示之含氟有機矽烷化合物,可例示出下列所示者。
(式中,b、c、d、e與上述相同)
本發明之表面改質劑,除了以上述式(1)所示之含氟有機矽烷化合物、其部分水解物或此等之部分水解縮合物之外,亦可包含溶劑或稀釋劑。該溶劑或稀釋劑,例如可列舉出醇類(乙醇、異丙醇等)、烴系溶劑(石油醚、礦油精、甲苯、二甲苯等)、酯系溶劑(乙酸乙酯、乙酸異丙酯、乙酸丁酯等)、醚系溶劑(二乙醚、異丙醚等)、酮系溶劑(丙酮、丁酮、甲基異丁酮等),較佳係使用醇、酯、醚、酮類等之極性溶劑,就溶解性、潤濕性、安全性等方面來看,特佳為異丙醇、甲基異丁酮。亦可較佳地使用氟系溶劑(全氟溶劑),該例子可列舉出氟化脂肪族烴系溶劑(全氟庚烷等)、氟化芳香族烴系溶劑(六氟化間二甲苯、三氟甲基苯等)、氟化醚系溶劑〔甲基全氟丁醚、乙基全氟丁醚、全氟(2-丁基四氫呋喃)、乙基九氟異丁醚、乙基九氟丁醚等〕,當中,就溶
解性、潤濕性等方面來看,可適合地使用氟化醚系溶劑。
上述溶劑可單獨使用1種或混合2種以上使用,不論何者,較佳係使用可均一地溶解上述成分者。
溶劑的用量並無特別限制,最適濃度因處理方法而有所不同,較佳係使用使該改質劑中的固體成分量成為0.05~5.0質量%,特佳成為0.1~1.0質量%之量。固體成分量係意味著非揮發成分的質量,當將後述硬化觸媒等添加於改質劑時,為式(1)之化合物、其部分水解物或此等之部分水解縮合物與此等之合計質量。
上述表面改質劑,當要求較快硬化速度時,可因應必要添加硬化觸媒。硬化觸媒的例子,可列舉出有機鈦酸酯、有機鈦螯合物、有機鋁化合物、有機鋯化合物、有機錫化合物、有機羧酸的金屬鹽、胺化合物及其鹽、四級銨化合物、鹼金屬的低級脂肪酸鹽、二烷基羥基胺、含有脈基之有機矽化合物、無機酸、全氟羧酸、全氟醇等,較佳係使用全氟羧酸。
硬化觸媒的添加量為觸媒量,相對於本發明之含氟有機矽烷化合物、其部分水解物或此等之部分水解縮合物100質量份,為0.05~5質量份,特佳為0.1~1質量份。
將如此得到之表面改質劑施予基材之方法,係有刷毛塗佈、浸泡、噴霧、蒸鍍處理等之一般所知的方法。
所施予之表面改質劑的處理溫度,其最適溫
度因施予方法而有所不同,例如在刷毛塗佈或浸泡時,較佳為10~200℃的範圍。處理濕度,就促進反應之方面來看,較佳係在加濕下進行。處理時間因溫度、濕度的條件而有所不同,較佳者,例如在室溫(23℃)、50%RH時,為24小時以上,在80℃)、80%RH時,為1小時以上。上述處理條件,較佳係因應基材、硬化觸媒等而適當地達到最適化。
由上述表面改質劑處理之基材並無特別限制,可為紙、布、金屬及其氧化物、玻璃、塑膠、陶瓷、石英等之各種材質者。本發明之表面改質劑,可將撥水撥油性賦予至前述基材。尤其可適合地使用作為經SiO2處理之玻璃或薄膜的表面改質劑。
形成於上述各種基材或物品表面之硬化被膜的膜厚,可因應基材的種類來適當地選擇,較佳為1~50nm,尤佳為3~20nm。
所得之被膜,係具有撥水撥油性、高滑水性,且與以往製品相比,其耐熱性、耐藥性、耐UV性等之耐久性優異。該特性,對於較常暴露在水或紫外線且不易維護之用途,或是容易附著油脂或指紋、化妝品、防日曬乳液、人或動物的排泄物、油等之用途乃為有效,例如可列舉出汽車、電車、船舶、飛機、高樓大廈等之窗玻璃或強化玻璃、頭燈燈罩、戶外用品、電話亭、戶外用大型顯示器、浴槽、洗手台般之衛生製品、化妝用具、廚房用建材、水槽、美術品等之賦予防指紋附著性之塗膜等。其
他,亦有用於作為CD、DVD等之防指紋附著塗膜、模具用的脫模劑或塗料添加劑、樹脂改質劑。此外,可列舉出汽車導航、行動電話、數位相機、數位攝影機、PDA、可攜式音訊播放器、汽車音響、遊戲機、眼鏡鏡片、相機鏡頭、鏡頭濾鏡、太陽眼鏡、胃視鏡等之醫療用機器、影印機、PC、液晶顯示器、有機電激發光顯示器、電漿顯示器、觸控面板顯示器、保護薄膜、抗反射薄膜等之光學物品。本發明之表面改質劑,由於可防止前述指紋及皮脂附著於前述物品,並可賦予抗損傷性,故特別有用於作為觸控面板顯示器、抗反射薄膜等之撥水撥油性。
以下係顯示合成例、實施例及比較例來具體地說明本發明,但本發明並不限定於下列實施例。下列例子中,數量平均分子量為依據凝膠滲透層析法(GPC)所求得之聚苯乙烯換算值,氟原子量為藉由19F-NMR所求取之值。
將以下列平均組成式(1a)所示之末端具有碘基之含氟化合物(數量平均分子量3,700、碘基濃度=0.026mol/100g)30g、過氧化二(三級丁基)1.12g、以下列式(2a)所示之含有乙烯基之矽烷化合物(乙烯基濃度=0.427mol/100g)7.3g、以及1,3-雙(三氟甲基)苯
30g,裝入於具備戴氏冷凝器(Dimroth Condenser)、滴入漏斗、溫度計、磁攪拌子之100mL的三頸燒瓶,並對燒瓶內部進行氮氣取代。一邊攪拌一邊於內溫100℃反應3小時,然後冷卻至室溫。接著加入鋅粉末1.02g與甲醇30g,一邊激烈攪拌一邊於內溫60℃反應12小時。以過濾器過濾反應液來去除固體成分,並於100℃/1mmHg的條件下進行汽提處理以去除溶劑成分、未反應矽烷及低沸點成分,而得到以下列式(3a)所示之生成物28g。從FT-IR、1H-NMR、19F-NMR中,可確認到末端碘基的消失、乙烯基的消失及甲氧基的存在。以式(3a)所示之生成物,其數量平均分子量為3,900,氟原子量為61質量%。
(e1/d1≒0.9、e1+d1≒38)
以與合成例1所記載者為相同配方,並使用以下列式(4a)所示之矽烷化合物(烯丙基濃度=0.329mol/100g)
9.5g來取代式(2a),而得到以下列式(5a)所示之生成物28g。以式(5a)所示之生成物,其數量平均分子量為3,900,氟原子量為61質量%。
(e1/d1≒0.9、e1+d1≒38)
以與合成例1所記載者為相同配方,並使用以下列式(6a)所示之含氟化合物(數量平均分子量4,100、碘基濃度=0.024mol/100g)30g來取代式(1a),而得到以下列式(7a)所示之生成物27g。以式(7a)所示之生成物,其數量平均分子量為4,300,氟原子量為67質量%。
(c1≒22)
將以下列平均組成式(8a)所示之末端具有烯丙基之含氟化合物(數量平均分子量3,700、烯丙基濃度=0.026mol/100g)30g、及以1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷對氯鉑酸進行改質後之觸媒的甲苯溶液(鉑濃度0.5質量%)0.05g,裝入於具備戴氏冷凝器、滴入漏斗、溫度計、磁攪拌子之100mL的三頸燒瓶,一邊攪拌一邊加溫至內溫80℃。於約5分鐘內將三甲氧矽烷(SiH基濃度=0.0082mol/g)1.2g滴入於滴入漏斗,於內溫80~90℃進行2小時的熟化。然後,於100℃/5mmHg的條件下進行汽提處理以去除殘餘的矽烷,而得到以下列式(9a)所示之生成物31g。從FT-IR、1H-NMR、19F-NMR中,可確認到烯丙基的消失及SiH基的消失。以式(9a)所示之生成物,其數量平均分子量為3,800,氟原子量為62質量%。
(e1/d1≒0.9、e1+d1≒38)
將以下列平均組成式(10a)所示之末端具有乙烯基之含氟化合物(數量平均分子量4,100、乙烯基濃度=0.024mol/100g)30g、及以1,3-二乙烯基-1,1,3,3-四甲基
二矽氧烷對氯鉑酸進行改質後之觸媒的甲苯溶液(鉑濃度0.5質量%)0.05g,裝入於具備戴氏冷凝器、滴入漏斗、溫度計、磁攪拌子之100mL的三頸燒瓶,一邊攪拌一邊加溫至內溫120℃。於約5分鐘內將以下列式(11a)所示之矽烷化合物(SiH基濃度=0.0036mol/g)3.0g滴入於滴入漏斗,於內溫110~120℃進行2小時的熟化。然後,於110℃/3mmHg的條件下進行汽提處理以去除殘餘的矽烷,而得到以下列式(12a)所示之生成物32g。從FT-IR、1H-NMR、19F-NMR中,可確認到乙烯基的消失及SiH基的消失。以式(12a)所示之生成物,其數量平均分子量為4,400,氟原子量為66質量%。
(c1≒22)
以使濃度成為0.1質量%之方式,將上述合成例1~3及比較合成例1、2中所得之生成物(氟系聚合物化合
物)溶解於Novec 7200(3M公司製、乙基全氟丁醚)而調製出處理浴。將化學強化玻璃(50mm×100mm、Corning公司製、商品名稱:Gorilla)浸漬於處理浴30秒後,以150mm/分的速度拉上,於80℃/80%RH的恆溫恆濕器內放置1小時而形成膜厚5~7nm的硬化被膜。
對於上述製作出之形成有硬化被膜之玻璃,使用接觸角計Drop Master(協和界面科學公司製),分別測定硬化被膜相對於水之接觸角(撥水性)及相對於油酸之接觸角(撥油性)。結果如表1所示。
於初期均顯示良好的撥水撥油性。
將上述製作出之形成有硬化被膜之玻璃放置在250℃的烤爐3小時後,以下列條件進行鋼絲絨磨耗2,000次
後,測定表面相對於水之接觸角(撥水性)。結果如表2所示。
鋼絲絨:BONSTAR#0000(Nippon Steel Wool公司製)
移動距離(單程):30mm
移動速度:1,600mm/分
荷重:1kg/cm2
於連結基具有醚鍵之比較例1,可觀察到接觸角的降低,可得知其耐熱性差。
使用金屬鹵化物燈,以輻射照度540W/m2(波長範圍300~400nm)將UV光照射至上述製作出之形成有硬化被膜之玻璃,照射240小時後,測定表面相對於水之接觸角(撥水性)。結果如表3所示。
於連結基具有醚鍵之比較例1,可觀察到接觸角的降
低,可得知其耐UV性差。
將上述製作出之形成有硬化被膜之玻璃浸漬在4.5質量%的氫氧化鉀水溶液(45℃)1小時〔處理(1)〕後,測定表面相對於水之接觸角(撥水性)。
此外,同樣將上述製作出之形成有硬化被膜之玻璃浸漬在1.0質量%的鹽酸水(23℃)72小時〔處理(2)〕後,測定表面相對於水之接觸角(撥水性)。
此等之結果如表4所示。
於連結基具有矽氧烷鍵之比較例2,可觀察到接觸角的降低,可得知其耐藥性差。
從上述實施例的結果中,可得知本發明之包含含有有機矽之氟聚合物化合物之表面改質劑,與以往製品相比,其耐熱性、耐UV性、耐藥性優異。
Claims (11)
- 一種表面改質劑,其係含有:以下列一般式(1)所示之含有有機矽之氟聚合物化合物、其部分水解物以及此等之部分水解縮合物的1種或2種以上,
- 如請求項1之表面改質劑,其中於一般式(1)中,h為2,k為2。
- 如請求項1之表面改質劑,其中於一般式(1)中,h為3,k為3。
- 如請求項1~3中任一項之表面改質劑,其中以一般式(1)所示之含有有機矽之氟聚合物化合物的數量平均分子量為500~50,000。
- 一種物品,其係經如請求項1~4中任一項之表面改質劑處理。
- 一種光學物品,其係經如請求項1~4中任一項之表面改質劑處理。
- 一種觸控面板,其係經如請求項1~4中任一項之表面改質劑處理。
- 一種抗反射薄膜,其係經如請求項1~4中任一項之表面改質劑處理。
- 一種SiO2處理玻璃,其係經如請求項1~4中任一項之表面改質劑處理。
- 一種強化玻璃,其係經如請求項1~4中任一項之表面改質劑處理。
- 一種石英基板,其係經如請求項1~4中任一項之表面改質劑處理。
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US7280731B2 (en) * | 2002-07-05 | 2007-10-09 | Silecs Oy | Stable organic-inorganic materials for waveguides, optical devices, and other applications |
JPWO2009008380A1 (ja) * | 2007-07-06 | 2010-09-09 | 旭硝子株式会社 | 表面処理剤、物品、および新規含フッ素エーテル化合物 |
JP5669257B2 (ja) * | 2009-10-27 | 2015-02-12 | 信越化学工業株式会社 | フルオロオキシアルキレン基含有ポリマー組成物および該組成物を含む表面処理剤並びに該表面処理剤で表面処理された物品 |
WO2011059430A1 (en) * | 2009-11-11 | 2011-05-19 | Essilor International | Surface treatment composition, process for producing the same, and surface-treated article |
JP5788852B2 (ja) * | 2011-11-01 | 2015-10-07 | 信越化学工業株式会社 | フルオロオキシアルキレン基含有ポリマー組成物、該組成物を含む表面処理剤、該表面処理剤で処理された物品及び光学物品 |
EP2915833B1 (en) * | 2012-11-05 | 2018-06-06 | Daikin Industries, Ltd. | Silane compound containing perfluoro(poly)ether group |
-
2014
- 2014-04-29 US US14/264,508 patent/US20140363682A1/en not_active Abandoned
- 2014-05-02 JP JP2014094931A patent/JP2015013983A/ja not_active Withdrawn
- 2014-06-02 KR KR20140066841A patent/KR20140143327A/ko not_active Application Discontinuation
- 2014-06-05 TW TW103119546A patent/TW201512245A/zh unknown
- 2014-06-06 CN CN201410247236.5A patent/CN104231893A/zh active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI711649B (zh) * | 2015-04-20 | 2020-12-01 | 日商信越化學工業股份有限公司 | 含氟聚醚之聚合物改質矽烷、表面處理劑及經處理物件 |
Also Published As
Publication number | Publication date |
---|---|
KR20140143327A (ko) | 2014-12-16 |
US20140363682A1 (en) | 2014-12-11 |
CN104231893A (zh) | 2014-12-24 |
JP2015013983A (ja) | 2015-01-22 |
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